Process for preparing organic compounds by a transition metal-catalysed cross-coupling reaction of an aryl-x, heteroaryl-x, cycloalkenyl-x or alkenyl-x compound with an alkyl, alkenyl, cycloalkyl or cycloalkenyl halide

This invention relates to a process for preparing functionalized aryl, heteroaryl, cycloalkenyl, or alkenyl compounds, by a transition-metal-catalyzed cross-coupling reaction of a substituted or unsubstituted aryl-X, heteroaryl-X, cycloalkenyl-X or alkenyl-X compound with an alkyl, alkenyl, cycloalkyl or cycloalkenyl halide, where X is a halide, diazonium, tosylate (p-toluenesulphonate), mesylate (methanesulphonate) or triflate (trifluoromethanesulphonate) leaving group.

Method for synthesis of secondary alcohols

A method for synthesis of secondary alcohols is provided for pharmaceutical secondary alcohol by addition of organoboronic acids with aldehydes in presence of the cobalt ion and bidentate ligands as the catalyst. In addition, an enantioselective synthesis method for secondary alcohols is also herein provided in the present invention. The present invention has advantages in using less expensive cobalt ion and commercially available chiral ligands as the catalyst, wide scope of organoboronic acids and aldehydes compatible with this catalytic reaction and achieving excellent yields and/or enantiomeric excess.

METHOD FOR THE PREPARATION OF PHOSPHINE BUTADIENE LIGANDS, COMPLEXES THEREOF WITH COPPER AND USE THEREOF IN CATALYSIS

A method for the creation of a carbon-carbon (C—C) bond or of a carbon-heteroatom (C-HE) bond includes reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) capable of replacing the leaving group, thus creating a C—C or C-HE bond, in which process the reaction is carried out in the presence of an effective amount of a catalytic system comprising at least one copper/butadienylphosphine complex. 1. A method for the creation of a carbon-carbon (C—C) bond or of a carbon-heteroatom (C-HE) bond by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) capable of replacing the leaving group , thus creating a C—C or C-HE bond , in which process the reaction is carried out in the presence of an effective amount of a catalytic system comprising at least one copper/butadienylphosphine complex.3. The method as claimed in claim 1 , in which the Rand Rsubstituents of the butadienylphosphine of formula (1) are identical and each represent a radical chosen independently from alkyl claim 1 , aryl claim 1 , heteroaryl claim 1 , monoalkylamino claim 1 , dialkylamino claim 1 , alkoxy claim 1 , aryloxy and heteroaryloxy.4. The method as claimed in claim 1 , in which the Rand/or Rsubstituents can be connected so as to form claim 1 , with the carbon atom which carries them claim 1 , a carbocyclic or heterocyclic group having from 3 to 20 carbon atoms which is saturated claim 1 , unsaturated claim 1 , monocyclic or polycyclic claim 1 , in the latter case comprising two or three rings claim 1 , it being possible for the adjacent rings to be aromatic in nature.5. The method as claimed in claim 1 , in which the butadienylphosphine of formula (1) is of Z configuration or of E configuration or is in the form of a mixture in all proportions of the Z and E configurations.6. The method as claimed in claim 1 , in which the butadienylphosphine of formula (1) exhibits the ...

Method of carrying out cc-coupling reactions

The present invention is directed to a method of carrying out Suzuki-Miyaura CC-coupling reactions, including reacting an aryl halide with an aryl boronic acid in an organic solvent in the presence of a carbon supported palladium catalyst and a base, wherein the reactions are carried out at constant pH. The invention is also directed to a palladium on carbon catalyst suitable for catalyzing Suzuki-Miyaura CC-coupling reactions.

Process for preparing styrene derivatives

A process is provided which allows the synthesis of a large number of styrene derivatives with formation of C—C bonds, with use being possible of economically advantageous substrates, readily available carbon nucleophiles, and both inexpensive and environmentally unproblematic catalyst systems, permitting reaction under mild conditions and a high compatibility with functional groups on the reactants involved.

Hydrocarbon Conversion Process Using a High Throughpout Process for Manufacturing Molecular Sieves

A method of crystallizing a crystalline molecular sieve having a pore size in the range of from about 2 to about 19 Å, said method comprising the steps of (a) providing a mixture comprising at least one source of ions of tetravalent element (Y), at least one hydroxide source (OH − ), and water, said mixture having a solid-content in the range of from about 15 wt. % to about 50 wt. %; and (b) treating said mixture to form the desired crystalline molecular sieve with stirring at crystallization conditions sufficient to obtain a weight hourly throughput from about 0.005 to about 1 hr −1 , wherein said crystallization conditions comprise a temperature in the range of from about 200° C. to about 500° C. and a crystallization time less than 100 hr.

New palladium catalyst, method for its preparation and its use

The invention relates to palladium(0) tris{tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine} complex of formula (I), as well as to its preparation and use. This compound is outstandingly stable, and can be used as catalyst with excellent results.

Compositions and processes of preparing and using the same

The present invention relates to compositions, for example, the DBU/Hexafluoroacetone hydrate salt, and processes of preparing and using the same for the modification of chemical compounds via the release of trifluoroacetate. The DBU/Hexafluoroacetone hydrate salt can perform trifluoromethylation reactions on chemical compounds, such as carbonyl group-containing compounds.

SYNTHESIS OF CYCLOPROPYL INDOLES AND CYCLOHEPTA[B]INDOLES, PHARMACEUTICAL COMPOSITIONS CONTAINING THEM AND METHOD OF USING THEM

Methods of making indole analogs using a rhodium-containing catalyst are described, along with methods of using the compounds to treat hyperglycemic, hyperlipidemic, or autoimmune disorders in mammals, and corresponding pharmaceutical compositions. Disclosed herein is a method of making indoles. The method comprises contacting a reactant of formula I wherein E is a protecting group, —SO2-Aryl, or —SO2-substituted-Aryl; and R and R2 are independently selected from the group consisting of hydrogen, halo, C1-C12-alkyl and aryl; with a rhodium(l)-containing catalyst. 2. The method of claim 1 , which yields a product mixture comprising a compound of formula (II).3. The method of claim 1 , which yields a product mixture comprising a compound of formula (III).4. The method of claim 1 , which yields a product mixture comprising a compound of formula (IV).5. The method of claim 1 , conducted in the absence of the alpha-alkene-containing co-reactant.7. The method of claim 1 , wherein the rhodium(I)-containing catalyst comprises [Rh(CO)Cl].8. The method of claim 7 , which yields a product mixture comprising a compound of formula (II).9. The method of claim 7 , which yields a product mixture comprising a compound of formula (III).10. The method of claim 7 , which yields a product mixture comprising a compound of formula (IV).11. The method of claim 7 , conducted in the absence of the alpha-alkene-containing co-reactant.13. The method of claim 1 , wherein the reactant of formula I is contacted with the catalyst in the presence of carbon monoxide.14. The method of claim 13 , which yields a product mixture comprising a compound of formula (II).15. The method of claim 13 , which yields a product mixture comprising a compound of formula (III).16. The method of claim 13 , which yields a product mixture comprising a compound of formula (IV).17. The method of claim 13 , conducted in the absence of the alpha-alkene-containing co-reactant.20. A pharmaceutical composition for treating ...

Compositions and methods for making alpha-(1,2)-branched alpha-(1,6) oligodextrans

Compositions for improving the health of a subject comprise alpha-(1,2)-branched alpha-(1,6) oligodextrans, preferably with an average molecular weight between about 10 kDa and 70 kDa, between about 10% and 50% alpha-(1,2)-osidic side chains, and having at least partial indigestibility in the subject. Methods for improving the health of a subject comprise administering the composition to a subject in an amount effective to improve gut health, or to prevent or treat a gastrointestinal disorder, a cholesterol-related disorder, diabetes, or obesity. Methods for making oligodextrans having controlled size and controlled degree of branching comprise providing alpha-(1,6) oligodextrans having an average molecular weight between 0.5 and 100 kDa and introducing at least 10% alpha-(1,2)-osidic side chains onto the alpha-(1,6) oligodextrans.

METHODS FOR PHOSPHINE OXIDE REDUCTION IN CATALYTIC WITTIG REACTIONS

A method for increasing the rate of phosphine oxide reduction, preferably during a Wittig reaction comprising use of an acid additive is provided. A room temperature catalytic Wittig reaction (CWR) the rate of reduction of the phosphine oxide is increased due to the addition of the acid additive is described. Furthermore, the extension of the CWR to semi-stabilized and non-stabilized ylides has been accomplished by utilization of a masked base and/or ylide-tuning.

ORGANIC REACTIONS CARRIED OUT IN AQUEOUS SOLUTION IN THE PRESENCE OF A HYDROXYALKYL(ALKYL)CELLULOSE OR AN ALKYLCELLULOSE

The present invention relates to a method of carrying out an organic reaction in aqueous solution in the presence of a hydroxyalkyl(alkyl)cellulose or an alkylcellulose. 1. A method of carrying out an organic reaction in a solvent containing at least 90% by weight , based on the total weight of the solvent , of water , which method comprises reacting the reagents in said solvent in the presence of a cellulose derivative as a surfactant which is selected from the group consisting of cellulose modified with one or more alkylene oxides or other hydroxyalkyl precursors , and alkylcellulose;where the organic reaction is not a polymerization or oligomerization reaction of olefinically unsaturated compounds; and [ a transition metal catalyzed C—C coupling reaction:', 'a transition metal catalyzed reaction involving C—N bond formation which is an Au-catalyzed cyclodehydratization of α,β-amino alcohols containing a C—C triple bond:', 'a transition metal catalyzed reaction involving C—O bond formation:', 'a transition metal catalyzed reaction involving C—S bond formation:', 'a transition metal catalyzed reaction involving C—B bond formation: or', 'a transition metal catalyzed reaction involving C-halogen bond formation; or, 'a transition metal catalyzed reaction in which a transition metal catalyst is used; where the transition metal catalyzed reaction is'}, 'a C—C coupling reaction not requiring transition metal catalysis which is selected from the group consisting of reactions of carbonyl or nitrile compounds and pericyclic reactions;, 'where the organic reaction is'}a nucleophilic substitution reaction;a reduction or an oxidation reaction; oran ester formation reaction or an ester hydrolysis reaction.2. The method as claimed in claim 1 , where the cellulose derivative has a viscosity of from 1 to 150000 mPa·s claim 1 , determined as a 2% by weight aqueous solution claim 1 , relative to the weight of water.3. The method as claimed in claim 1 , where in the cellulose ...

Polycyclic aromatic compounds and methods for making and using the same

Disclosed herein are embodiments of polycyclic aromatic compounds and methods of making and using the same. Various different types of polycyclic ring systems are disclosed, including, but not limited to, polymeric aromatic compounds (e.g., nanographene compounds), pentacene-like compounds, chiral aromatic compounds, asymmetric arene compounds formed from naphthalene-, anthracene-, phenanthrene-, and pyrene-based starting compounds, and dimerized aromatic compounds. Also disclosed herein are novel benzannulation-based methods for making the disclosed polycyclic aromatic compounds.

AROMATIC COMPOUNDS FROM FURANICS

Described are methods for preparing phenols, benzene carboxylic acids, esters and anhydrides thereof from furanic compounds by reaction with a dienophile, wherein the furanic compounds are reacted with a hydrazine and/or oxime and then reacted with a dienophile. 2. The method according to claim 1 , wherein said compound having a backbone comprising formula (II) is furfural claim 1 , furan-2 claim 1 ,5-dicarbaldehyde claim 1 , methoxymethylfurfural claim 1 , chloromethylfurfural claim 1 , 5-hydroxymethylfurfural claim 1 , or a mixture thereof.3. The method according to claim 1 , wherein the compound having a backbone comprising formula (I) is a phenol claim 1 , a hydroxyl tricarboxylic acid claim 1 , a hydroxyl dicarboxylic acid claim 1 , a hydroxyl carboxylic acid claim 1 , a benzene dicarboxylic acid claim 1 , a benzene tricarboxylic acid claim 1 , or a benzene tetracarboxylic acid claim 1 , or an ester claim 1 , ether or anhydride thereof.4. The method according to claim 1 , wherein the reaction of step (ii) is catalyzed by a Lewis acid claim 1 , Brønsted acid claim 1 , or a combination thereof.5. The method according to claim 1 , wherein the dienophile is ethylene.6. The method according to claim 5 , wherein the compound having a backbone comprising formula (II) is 5-hydroxymethylfurfural claim 5 , 5-methoxymethylfurfural claim 5 , 5-chloromethylfurfural or 2 claim 5 ,5-furandicarboxaldehyde claim 5 , and the compound having a backbone comprising formula (I) is terephthalic acid.7. The method according to claim 6 , wherein step (ii) further comprises a catalyst that is a Brønsted acid and/or a Lewis acid supported on a solid material.8. The method according to claim 6 , wherein the compound having a backbone comprising formula (II) is furfural and the compound having a backbone comprising formula (I) is phenol or an ester thereof.9. The method according to claim 1 , wherein the dienophile is an alkyne.10. The method according to claim 9 , wherein the compound ...

Gold-Catalyzed C-C Cross-Coupling of Boron- and Silicon-Containing Aryl Compounds and Aryldiazonium Compounds by Visible-Light

The present invention relates to a method for producing (functionalized) biaryls by employing a visible-light-driven, gold-catalyzed C—C cross-coupling reaction system involving boron- and silicon-containing aryl compounds and aryldiazonium compounds. Moreover, the present invention relates to the use of such boron- and silicon-containing aryl compounds and aryldiazonium compounds, as well as related gold catalysts, in the manufacture of (functionalized) biaryls. 6. The method according to claim 1 , wherein Ris selected from BF claim 1 , PF claim 1 , SbF claim 1 , OTf claim 1 , NTf claim 1 , OSOCF claim 1 , F claim 1 , OSOF claim 1 , BArF claim 1 , BArF claim 1 , brosylate claim 1 , carborane claim 1 , C(TF) claim 1 , B(Ph) claim 1 , Altebat claim 1 , Bortebat claim 1 , PFTB claim 1 , and C(CF).7. The method according to claim 1 , wherein the aryl groups Arand Arare independently selected from furanyl claim 1 , pyrrolyl claim 1 , thiophenyl claim 1 , imidazolyl claim 1 , pyrazolyl claim 1 , oxazolyl claim 1 , isoxazolyl claim 1 , thiazolyl claim 1 , phenyl claim 1 , pyridinyl claim 1 , pyrazinyl claim 1 , pyrimidinyl claim 1 , pyradizinyl claim 1 , benzofuranyl claim 1 , indolyl claim 1 , benzothiophenyl claim 1 , benzimidazolyl claim 1 , indazolyl claim 1 , benzoxazolyl claim 1 , benzisoxazolyl claim 1 , benzothiazolyl claim 1 , isobenzofuranyl claim 1 , isoindolyl claim 1 , purinyl claim 1 , naphthyl claim 1 , chinolinyl claim 1 , chinoxalinyl and chinazolinyl.8. The method according to claim 1 , wherein each of the aryl groups Arand Arof the boron- or silicon-containing aryl compounds and the aryldiazonium compound claim 1 , respectively claim 1 , comprises one or more substituents which are independently selected from the group consisting of hydrogen claim 1 , halogen claim 1 , nitro claim 1 , hydroxy claim 1 , cyano claim 1 , carboxyl claim 1 , C-Ccarboxylic acid ester claim 1 , C-Cether claim 1 , C-Caldehyde claim 1 , C-Cketone claim 1 , sulfonyl claim 1 , C- ...

HARDMASK COMPOSITION, METHOD OF FORMING PATTERN BY USING THE HARDMASK COMPOSITION, AND HARDMASK FORMED USING THE HARDMASK COMPOSITION

Provided are a hardmask composition, a method of forming a pattern using the hardmask composition, and a hardmask formed using the hardmask composition. The hardmask composition includes a polar nonaqueous organic solvent and one of: i) a mixture of graphene quantum dots and at least one selected from a diene and a dienophile, ii) a Diels-Alder reaction product of the graphene quantum dots and the at least one selected from a diene and a dienophile, iii) a thermal treatment product of the Diels-Alder reaction product of graphene quantum dots and the at least one selected from a diene and a dienophile, or iv) a combination thereof. 1. A hardmask composition comprising: a mixture of graphene quantum dots and at least one selected from a diene and a dienophile,', 'a Diels-Alder reaction product of the graphene quantum dots and the at least one selected from a diene and a dienophile,', 'a thermal treatment product of the Diels-Alder reaction product of the graphene quantum dots and the at least one selected from a diene and a dienophile, or', 'a combination thereof; and, 'one of,'}a polar nonaqueous organic solvent.2. The hardmask composition of claim 1 , whereinthe graphene quantum dots include at an end thereof at least one first functional group, andthe at least one first functional group is selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an epoxy group, and an amine group.3. The hardmask composition of claim 1 , wherein the diene and the dienophile include a second functional group that is the same as or similar to that of the polar nonaqueous organic solvent.4. The hardmask composition of claim 3 , wherein the second functional group is at least one selected from the group consisting of a C1-C20 alkenylene group including a carboxyl group claim 3 , an organic group including a carbonyl group claim 3 , an organic group including —COOR (wherein R is a C1-C20 alkyl group or a C2-C20 alkenyl group) claim 3 , a hydrogenated C1 ...

Treatment of quarry liquid effluent

Disclosed is a method for preparing a solid material including manganese, the method including the following steps: a. bringing into contact an aqueous effluent including manganese, for example at least 5 mg/L, typically at least 5 to 50 mg/L, and preferably 7 to 25 mg/L of manganese, with an oxidizing agent, manganese, preferably at a temperature between 10° C. and 50° C., and obtaining an oxidized aqueous solution; b. adding a base to the oxidized aqueous solution obtained at the end of step a) until a pH of between 8 and 12, preferably greater than 9, and preferably from 9 to 10.5, and obtaining a solution including a precipitate; c. filtration of the solution obtained at the end of step b); and d. obtaining a solid material including manganese, and especially manganese (IV) and/or Mn (III).

METHODS FOR ENANTIOSELECTIVE ALLYLIC ALKYLATION OF ESTERS, LACTONES, AND LACTAMS WITH UNACTIVATED ALLYLIC ALCOHOLS

The present disclosure provides methods for enantioselective synthesis of cyclic and acyclic α-quaternary carboxylic acid derivatives via nickel-catalyzed allylic alkylation. 113-. (canceled)15. The method of claim 14 , wherein:{'sub': '2', 'the Ni(0) source is Ni(COD);'}L is (S)—C3-TunePhos; andthe organic solvent is diethyl ether.16. The method of claim 14 , wherein:{'sub': '6', 'Ris methyl; and'}{'sub': '7', 'Ris methyl.'}17. (canceled)18. The method of claim 15 , wherein:{'sub': '6', 'Ris methyl; and'}{'sub': '7', 'Ris methyl.'}19. A method comprising{'claim-ref': {'@idref': 'CLM-00014', 'claim 14'}, 'preparing a compound of Formula (XI) according to ; and'}synthesizing a pharmaceutical agent from the compound of Formula (XI).21. The method of claim 20 , wherein:{'sub': '2', 'the Ni(0) source is Ni(COD);'}L is (S)—C3-TunePhos; andthe organic solvent is diethyl ether.22. The method of claim 20 , wherein:{'sub': '6', 'Ris methyl; and'}{'sub': '7', 'Ris methyl.'}23. The method of claim 21 , wherein:{'sub': '6', 'Ris methyl; and'}{'sub': '7', 'Ris methyl.'} This Application claims the benefit of U.S. Provisional Application 62/580,091, filed Nov. 1, 2017, the contents of which are hereby incorporated herein by reference.This invention was made with government support under Grant Nos. GM080269 awarded by the National Institutes of Health. The Government has certain rights in the invention.Synthetic methods for the generation of enantioenriched quaternary stereocenters are highly desirable given their prevalence as motifs in a wide variety of biologically active molecules of both natural and unnatural origin, and the pharmaceutical industries increasing recognition for the motif's applicability in drug design. Despite their importance, the number of highly enantioselective transformations that construct quaternary stereocenters under mild reaction conditions is limited, with respect to both cyclic and acyclic systems.Since 1965, transition metal-catalyzed allylic ...

NOVEL NICKEL CATALYST, PROCESS FOR PREPARATION AND USE THEREOF

The present invention disclosed to a novel nickel catalyst of formula (I) process for preparation of the same and use of nickel catalyst of formula (I) for C—H bond alkylation, and benzylation of heteroarenes. 2. The compound as claimed in claim 1 , wherein said nickel catalyst of formula (I) is selected from (NNN)-H [2-(diethylamino)-N-(quinolin-8-yl)acetamide] claim 1 , (NNN)NiCl [2-(diethylamino)-N-(quinolin-8-yl)acetamide](NiCl) claim 1 , (NNN)Ni(OAc) [2-(diethylamino)-N-(quinolin-8-yl)acetamide]Ni(OAc).3. A process for the preparation of nickel catalyst of formula (I) as claimed in claim 1 , wherein said process comprising the steps of:{'sup': R2', '8-Quin, 'a) Refluxing the reaction mixture of 2-bromo-N-(quinolin-8-yl) acetamide and amino compound in solvent for the period ranging from 20 to 24 hrs at temperature ranging from 60 to 80° C. afford (NNN)-H [2-(dialkylamino)-N-(quinolin-8-yl)acetamide] Ligand;'}b) Adding triethylamine to the mixture of compound of step (a), nickel compound and solvent followed by refluxing the reaction mixture for the period in the range of 3 to 12 hrs at a temperature ranging from 60 to 70° C. to afford nickel catalyst of formula (I).4. The process as claimed in claim 3 , wherein said amino compound is selected from diisopropyl amine claim 3 , diethylamine claim 3 , dimethyl amine claim 3 , morpholine claim 3 , N-methyl piperazine claim 3 , cyclopentyl amine claim 3 , cyclohexyl amine and said nickel compound is selected from (DME)NiCl claim 3 , (THF)NiBr claim 3 , Ni(OAc).5. The process as claimed in claim 3 , wherein said solvent in step (a) and (b) is selected from acetone or tetrahydrofuran (THF).6. A process for the alkylation or benzylation of heteroarene using nickel catalyst of formula (I) as claimed in claim 1 , comprising stirring the reaction mixture of heteroarene claim 1 , organic halide compound or benzyl compound claim 1 , catalyst of formula (I) claim 1 , base and solvent at temperature ranging from 120 to 160° C. ...

INTRODUCTION OF ALKYL SUBSTITUENTS TO AROMATIC COMPOUNDS

Novel selective synthesis route to introduce primary alkyl groups on aromatic compounds is disclosed. The synthesis route is based on electrophilic aromatic substitutions of thionium ion species that are generated in-situ from aldehydes and thiols, affording benzyl sulfide that can be reduced with triethylsilane. 2. The process of claim 1 , wherein Ris ethyl.3. The process of claim 1 , wherein said acidic catalyst is one or more Lewis acid selected from the group consisting of: CuCl claim 1 , Sc(OTf) claim 1 , Fe(OTf) claim 1 , In(OTf) claim 1 , BF3.OEt claim 1 , and Cu(OTf).4. The process of claim 1 , wherein said acidic catalyst is one or more Brønsted acids selected from the group consisting of: Triflic acid (TfOH) claim 1 , para-toluenesulfonic acid claim 1 , and trifluoroacetic acid.5. The process of claim 1 , wherein said suitable solvent is a polar solvent selected from the group consisting of: acetonitrile claim 1 , nitromethane claim 1 , and 2 claim 1 ,2 claim 1 ,2-trifluoroethanol (TFE) claim 1 , hexafluoroisopropanol (HFIP) or a mixture thereof.6. The process of claim 1 , characterized by at least 30% yield of the compound represented by Formula I.8. The process of claim 7 , wherein said reducing agent is a silane.9. The process of claim 8 , wherein said silane is EtSiH.14. A pharmaceutical composition comprising a product according to and a pharmaceutically acceptable excipient.15. A composition comprising:{'sub': 2', '3', '3', '3', '3', '2', '2, '(i) one or more Lewis acids selected from the group consisting of: CuCl, Sc(OTf), Fe(OTf), In(OTf), BF.OEt, TfOH and Cu(OTf);'}(ii) a polar solvent selected from the group consisting of: acetonitrile, nitromethane, and 2,2,2-trifluoroethanol (TFE), or a mixture thereof; and(iii) RSH, wherein R is selected from the group consisting of: alkyl, benzyl, alkoxy, aryloxy, carbonyl, and carboxy, substituted or non-substituted.16. The composition of claim 15 , wherein said Lewis acid is in a molar concentration of at ...

METHOD FOR PRODUCING 1-(4-HYDROXYPHENYL)-4-(4-TRIFLUOROMETHOXYPHENOXY)PIPERIDINE OR SALT THEREOF

The present invention provides a method for producing 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof, the method including the step of heating hydroquinone and 4-(4-trifluoromethoxyphenoxy)piperidine. This method can produce 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof in an industrially advantageous manner. 2. The production method according to claim 1 , wherein the hydroquinone represented by Formula (2) or a salt thereof is used in an amount of 2 to 10 moles per mole of the 4-(4-trifluoromethoxyphenoxy)piperidine represented by Formula (3) or a salt thereof.3. The production method according to claim 1 , wherein the heating step comprises heating at 150° C. or more.4. The production method according to claim 1 , wherein the heating step is performed under solvent-free conditions.9. A method for producing the compound represented by Formula (9) or a salt thereof by using 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof claim 1 ,the method comprising:{'claim-ref': {'@idref': 'CLM-00006', 'claim 6'}, 'steps (c2) and (c3) according to .'}10. A method for producing the compound represented by Formula (9) or a salt thereof by using 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof claim 1 ,the method comprising:{'claim-ref': {'@idref': 'CLM-00007', 'claim 7'}, 'steps (c1), (c2), and (c3) according to .'}11. A method for producing the compound represented by Formula (9) or a salt thereof by using 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof claim 1 ,the method comprising:{'claim-ref': {'@idref': 'CLM-00008', 'claim 8'}, 'step (b1) according to .'} The present invention relates to a method for producing 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof, and use thereof.1-(4-Hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine and salts thereof are compounds that are useful as an ...

An improved process for the preparation of clobazam and its intermediate

The present invention provides an improved process for the preparation of 8-chloro-1-phenyl-1H-benzo[b][1,4]diazepine-2,4(3H,5H)-dione (hereafter referred to as the compound (IV)), which is useful as a key intermediate for the synthesis of Clobazam (referred to as the compound (I)) 7-chloro-1-methyl-5-phenyl-1H-benzo[b][1,4]diazepine-2,4(3H,5H)-dione. The process of the present invention further involves transformation of the compound (IV) into Clobazam (I), comprising (a) reacting the compound (II) (as described herein) with monoalkyl malonate in the presence of a coupling agent to obtain the compound (III) (as described herein); followed by the cyclization using a base; (b) reacting the compound-IV (as described herein) obtained from step (a) with methylating agent. The process of the present invention involves formation of novel intermediates methyl 3-((4-chloro-2-(phenylamino) phenyl)amino)-3-oxopropanoate (IIIa) and 3-((4-chloro-2-(phenylamino)phenyl)amino)-3-oxopropanoic acid (V).

LIGAND, NICKEL COMPLEX COMPRISING THE LIGAND, AND REACTION USING THE NICKEL COMPLEX

An object of the present invention is to provide a method for directly performing arylation (particularly α-arylation) of carbonyl or thiocarbonyl compounds using a more inexpensive phenol derivative and nickel catalyst. Another object of the present invention is to provide a novel nickel catalyst that can be used in this method, and a novel ligand of the nickel catalyst. The novel compounds of the present invention are a compound having a diphosphine skeleton in which a five- or six-membered heterocyclic ring is substituted with two dialkylphosphines and/or dicycloalkylphosphines, or a salt thereof, and a compound having the diphosphine skeleton that is bound to nickel. Moreover, coupling reaction of a carbonyl compound and a phenol derivative can be advanced in the presence of a nickel compound having a monodentate or bidentate dialkylphosphine and/or dicycloalkylphosphine skeleton. 1. A compound having a diphosphine skeleton in which a five- or six-membered heterocyclic ring is substituted with two dialkylphosphines and/or dicycloalkylphosphines , or a salt thereof.3. The compound or a salt thereof according to claim 2 , wherein Rto Rin Formula (1) are the same or different claim 2 , and each is optionally substituted cycloalkyl.4. The compound or a salt thereof according to claim 1 , which is used to produce a catalyst for coupling reaction of a carbonyl compound and a phenol derivative.5. A compound having a diphosphine skeleton in which a five- or six-membered heterocyclic ring is substituted with two dialkylphosphines and/or dicycloalkylphosphines claim 1 , the diphosphine skeleton being bound to nickel.7. The compound according to claim 6 , wherein Rto Rin Formula (2) are the same or different claim 6 , and each is optionally substituted cycloalkyl.8. The compound according to claim 5 , which is a catalyst for coupling reaction of a carbonyl compound and a phenol derivative.9. A method for producing an arylcarbonyl compound claim 5 ,{'claim-ref': {'@idref': ...

Complexes

The present invention provides a palladium(II) complex of formula (1) or a palladium(II) complex of formula (2). 2. The process of claim 1 , wherein E is P.3. The process of claim 2 , wherein Rand Rare less sterically bulky than a cyclohexyl group when R claim 2 , R claim 2 , R claim 2 , Rand/or Rare more sterically bulky than a cyclohexyl group.4. The process of claim 1 , wherein R claim 1 , R claim 1 , Rand Rare —H.5. The process of claim 1 , wherein two of R claim 1 , R claim 1 , Rand Rare —H claim 1 , and the other two of R claim 1 , R claim 1 , Rand Rare claim 1 , independently claim 1 , unsubstituted straight-chain alkyl claim 1 , unsubstituted branched-chain alkyl claim 1 , unsubstituted cycloalkyl claim 1 , or unsubstituted alkoxy.6. The process of claim 1 , wherein three of R claim 1 , R claim 1 , R claim 1 , Rand Rare —H claim 1 , and the other two of R claim 1 , R claim 1 , R claim 1 , Rand Rare claim 1 , independently claim 1 , unsubstituted straight-chain alkyl claim 1 , unsubstituted branched-chain alkyl claim 1 , unsubstituted cycloalkyl claim 1 , unsubstituted alkoxy claim 1 , unsubstituted —N(alkyl) claim 1 , wherein the alkyl groups are independently straight-chain or branched-chain groups claim 1 , or unsubstituted —N(aryl) claim 1 , wherein the aryl groups are the same or different; or{'sub': 7', '8', '9', '10', '11', '7', '8', '9', '10', '11', '2', '2, 'wherein two of R, R, R, Rand Rare —H, and the other three of R, R, R, Rand Rare, independently, unsubstituted straight-chain alkyl, unsubstituted branched-chain alkyl, unsubstituted cycloalkyl, unsubstituted alkoxy, unsubstituted —N(alkyl), wherein the alkyl groups are independently straight-chain or branched-chain groups, or unsubstituted —N(aryl), wherein the aryl groups are the same or different.'}8. The process according to claim 1 , wherein X is a halo group or a trifluoroacetate group.11. The process of claim 10 , wherein E is P.12. The process of claim 11 , wherein Rand Rare less ...

DIRECT ANTI-MARKOVNIKOV ADDITION OF ACIDS TO ALKENES

A method of making an anti-Markovnikov addition product, comprises reacting an acid with an alkene or alkyne in a dual catalyst reaction system to the exclusion of oxygen to produce said anti-Markovnikov addition product; the dual catalyst reaction system comprising a single electron oxidation catalyst in combination with a hydrogen atom donor catalyst. Dual catalyst composition useful for carrying out such methods are also described. 1. A method of making an anti-Markovnikov addition product , comprising:reacting an acid with an alkene or alkyne in a dual catalyst reaction system to the exclusion of oxygen to produce said anti-Markovnikov addition product;said dual catalyst reaction system comprising a single electron oxidation catalyst in combination with a hydrogen atom donor catalyst;wherein said hydrogen atom donor catalyst is a compound of the Formula A-SH, where A is alkyl, aryl, or an electron withdrawing group.2. The method of claim 1 , wherein said anti-Markovnikov addition product is produced regio selectively in a ratio of at least 5:1 of anti-Markovnikov addition product as compared to the corresponding Markovnikov addition product.3. The method of claim 1 , wherein A is selected from the group consisting of alkyl claim 1 , aryl claim 1 , carboxyl claim 1 , and carbonyl groups.4. The method of claim 1 , wherein said single electron oxidation catalyst is a photocatalyst.5. The method of claim 4 , wherein said photocatalyst comprises a carbocyclic or heterocyclic aromatic compound containing ring nitrogen heteroatoms.6. The method of claim 5 , wherein said photocatalyst comprises an anthracene claim 5 , aza-anthracene or polyaza-anthracene nucleus which is unsubstituted claim 5 , substituted or polysubstituted at any position with halogen claim 5 , and/or with one or more lower alkyl or cycloalkyl radicals claim 5 , and/or with other phenyl substituents.7. The method of claim 4 , wherein said photocatalyst has a reduction potential of about −1.0 V to +0.1 ...

PROCESS FOR PREPARING CHLORINATED BIPHENYLANILIDES AND BIPHENYLANILINES

The present invention relates to a process for preparing substituted biphenylanilides of the formula (I) 2. Process according to claim 1 , wherein the compound (II) is selected from the group consisting of N-(2-bromo-4-fluorophenyl)acetamide claim 1 , N-(2-bromophenyl)acetamide claim 1 , N-(2-bromophenyl)-3-oxobutanamide claim 1 , N-(2-bromo-4-fluorophenyl)-3-oxobutanamide claim 1 , 2-bromo-N-(propan-2-ylidene)aniline claim 1 , 2-bromo-4-fluoro-N-(propan-2-ylidene)aniline claim 1 , 2-bromo-4-fluoroaniline claim 1 , 2-bromoaniline.3. Process according to claim 1 , wherein the compound of the formula (III) is selected from the group consisting of bis(3 claim 1 ,4-dichlorophenyl)borinic acid claim 1 , bis(2 claim 1 ,3-dichlorophenyl)borinic acid claim 1 , bis(3-dichlorophenyl)borinic acid claim 1 , bis(4-dichlorophenyl)borinic acid claim 1 , 4-chlorophenylboronic acid claim 1 , 3-chlorophenylboronic acid claim 1 , 2-chlorophenylboronic acid claim 1 , 3 claim 1 ,4-dichlorophenylboronic acid and 2 claim 1 ,3-dichlorophenylboronic acid.4. Process according to claim 1 , wherein the base is selected from alkali metal hydroxides claim 1 , alkali metal carbonates and alkali metal hydrogencarbonates.5. Process according to claim 1 , wherein the palladium catalyst a) is a complex of palladium in the 0 oxidation state and a phosphine ligand of the formula (V) or a salt thereof.6. Process according to claim 1 , wherein a palladium catalyst b) is used.7. Process according to claim 1 , wherein a palladium catalyst c) is used claim 1 , and this palladium catalyst c) comprises or consists of metallic palladium on activated carbon in the presence of a phosphine ligand of formula (V) or a salt thereof.8. Process according to claim 6 , wherein the salt of the palladium catalyst b) is selected from the group consisting of palladium chloride claim 6 , palladium acetate claim 6 , palladium acetylacetonate and bis(acetonitrile)palladium chloride.9. Process according to claim 1 , wherein the ...

Method for preparing aromatic amino acid derivative

The present invention provides methods of efficiently producing various optically active aromatic amino acid derivatives by reacting, using an additive, a specific ester compound with an aromatic halide and zinc in the presence of a catalyst. The present invention also provides amino acid derivatives that can be produced by the methods.

NANO-TO-NANO FE/PPM Pd CATALYSIS OF CROSS-COUPLING REACTIONS IN WATER

In one embodiment, the present application discloses a catalyst composition comprising: a) a reaction solvent or a reaction medium; b) organometallic nanoparticles comprising: i) a nanoparticle (NP) catalyst, prepared by a reduction of an iron salt in an organic solvent, wherein the catalyst comprises at least one other metal selected from the group consisting of Pd, Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or mixtures thereof; c) a ligand; and d) a surfactant; wherein the metal or mixtures thereof is present in less than or equal to 50,000 ppm relative to the iron salt. 120.-. (canceled)22. The method of claim 21 , wherein the metal claim 21 , other than Pd claim 21 , is selected from the group consisting of Pt claim 21 , Au claim 21 , Ni claim 21 , Co claim 21 , Cu claim 21 , Mn claim 21 , Rh claim 21 , Ir claim 21 , Ru and Os or a mixture thereof.23. The method of further comprising:iii) contacting the product mixture with an organic solvent to form an organic phase and an aqueous phase; andiv) separating the organic phase from the aqueous phase containing the micelle composition as well as the iron/ppm Pd nanoparticles.24. The method of further comprising:v) re-cycling the aqueous phase containing the micelle composition and Fe/ppm Pd nanoparticles for use in a subsequent cross coupling or other reactions.25. The method of claim 21 , wherein the reaction solvent is water claim 21 , and the reaction solvent further comprising an organic solvent claim 21 , wherein the organic co-solvent is present in at least 5% claim 21 , 10% claim 21 , 20% claim 21 , 30% claim 21 , 40% claim 21 , 50% claim 21 , 70% claim 21 , 80% or at least 90% wt/wt.2611. The method of claim claim 21 , wherein the organic co-solvent is present at a wt of organic co-solvent to the wt of water (wt/wt) of 1/10 claim 21 , 2/10 claim 21 , 5/10 claim 21 , 10/10 claim 21 , 20/10 claim 21 , 30/10 claim 21 , 50/10 claim 21 , 70/10 claim 21 , 90/10 claim 21 , 100/10 claim 21 , 200/10 claim 21 , 300/10 ...

Methods of carbon-carbon bond fragmentation

The present disclosure relates to methods of carbon-carbon bond fragmentation.

High Throughput Process for Manufacturing Molecular Sieves of MFI Framework Type

A process for converting hydrocarbons comprising the step of contacting said hydrocarbons under conversion conditions with a crystalline molecular sieve having a pore size in the range of from about 2 to about 19 Å, said molecular sieve made by a method comprising the steps of (a) providing a mixture comprising at least one source of ions of tetravalent element (Y), at least one trivalent element hydroxide source (OH), and water, said mixture having a solid-content in the range of from about 15 wt. % to about 50 wt. % .%, preferably of from about 20% to about 30%; and (b) treating said mixture to form the desired crystalline molecular sieve with stirring at crystallization conditions sufficient to obtain a weight hourly throughput from about 0.005 to about 1 hr, wherein said crystallization conditions comprise a temperature in the range of from about 200° C. to about 500° C. and a crystallization time less than 100 hr, wherein said crystalline molecular sieve has a zeolite framework type of MFI. 2. The process recited in claim 1 , wherein said crystalline molecular sieve formed in step (b) is substantially free of non-crystalline material.3. The process recited in claim 1 , wherein said weight hourly throughput is in the range of from about 0.008 to about 1 hr.4. The process recited in wherein the mixture comprises a structure-directing agent for the molecular sieve.5. The process recited in claim 1 , wherein said temperature range is from about 225° C. to about 250° C.6. The process recited in claim 1 , wherein said mixture further comprises from about 0.01 to 20 wt. % based on the total weight of said mixture of at least one seed source.7. The process recited in claim 1 , wherein said trivalent element is aluminum.8. The process recited in claim 1 , wherein said crystallization temperature is in the range of from about 200° C. to about 300° C. claim 1 , and crystallization time is less than 72 hr.9. The process recited in claim 1 , wherein said crystallization ...

ETHYLENE-TO-LIQUIDS SYSTEMS AND METHODS

The present disclosure provides petrochemical processing methods and systems, including ethylene conversion processes and systems, for the production of higher hydrocarbon compositions, for example liquid hydrocarbon compounds, with reduced amount of unsaturated hydrocarbons. 1. A method for generating hydrocarbon compounds with eight or more carbon atoms (C compounds) , comprising:{'sub': 2+', '2+', '3+, '(a) directing a feed stream comprising unsaturated C hydrocarbon compounds into an oligomerization unit that permits at least a portion of said unsaturated C hydrocarbon compounds to react in an oligomerization process to yield an effluent comprising unsaturated C hydrocarbon compounds; and'}{'sub': 3+', '8+, '(b) directing at least a portion of said effluent from said oligomerization unit and a stream comprising isoparaffins into an alkylation unit downstream of and separate from said oligomerization unit, which alkylation unit permits at least a portion of said unsaturated C hydrocarbon compounds and said isoparaffins to react in an alkylation process to yield a product stream comprising said C compounds.'}2. The method of claim 1 , further comprising: directing methane and an oxidizing agent into an oxidative coupling of methane (OCM) unit that facilitates an OCM reaction to generate an OCM product stream comprising ethylene (CH) claim 1 , and wherein at least a portion of said feed stream is provided by the OCM product stream.3. The method of claim 1 , wherein the oligomerization unit comprises a dimerization unit and the oligomerization process comprises a dimerization process claim 1 , and wherein the dimerization process operates at a temperature of 20° C. to 200° C. and a pressure of 100 psia to 400 psia.4. The method of claim 1 , wherein the product stream is an alkylate stream comprising an alkylate product comprising saturated C hydrocarbon compounds claim 1 , isomers thereof claim 1 , or both saturated C hydrocarbon compounds and isomers thereof.5. The ...

COMPLEXES

A palladium(II) complex of formula (1) or a palladium(II) complex of formula (3). 2. A palladium(II) complex according to claim 1 , wherein E is P.3. A palladium(II) complex according to claim 1 , wherein Rand Rare independently selected from the group consisting of substituted and unsubstituted straight-chain alkyl claim 1 , substituted and unsubstituted branched-chain alkyl claim 1 , substituted and unsubstituted cycloalkyl claim 1 , substituted and unsubstituted aryl claim 1 , and substituted and unsubstituted heteroaryl wherein the heteroatoms are independently selected from sulfur claim 1 , nitrogen and oxygen.4. A palladium(II) complex according to claim 1 , wherein R claim 1 , R claim 1 , Rand Rare independently selected from the group consisting of —H claim 1 , substituted and unsubstituted straight-chain alkyl claim 1 , substituted and unsubstituted branched-chain alkyl claim 1 , substituted and unsubstituted cycloalkyl claim 1 , substituted and unsubstituted alkoxy claim 1 , substituted and unsubstituted aryl claim 1 , substituted and unsubstituted heteroaryl claim 1 , substituted and unsubstituted —N(alkyl)(wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched-chain groups) claim 1 , substituted and unsubstituted —N(cycloalkyl)(wherein the cycloalkyl groups may be the same or different) claim 1 , substituted and unsubstituted —N(aryl)(wherein the aryl groups may be the same or different) claim 1 , substituted and unsubstituted —N(heteroaryl)(wherein the heteroaryl groups may be the same or different) and substituted and unsubstituted heterocycloalkyl groups.5. A palladium(II) complex according to claim 4 , wherein each of R claim 4 , R claim 4 , Rand Rare —H.6. A palladium(II) complex according to claim 4 , wherein each of R claim 4 , R claim 4 , Rand Rare independently straight-chain alkyl groups claim 4 , preferably -Me.7. A palladium(II) complex according to claim 1 , wherein two of R claim ...

STRUCTURED PHOTOCATALYST, STRUCTURED PHOTOCATALYST COMPOSITION, PHOTOCATALYST COATED MATERIAL, METHOD FOR PRODUCING STRUCTURED PHOTOCATALYST, AND METHOD FOR DECOMPOSING ALDEHYDES

An object of the present disclosure is to provide a structured photocatalyst that can effectively prevent aggregation of photocatalyst particles and maintain favorable photocatalytic functionality over a long period of time. A structured photocatalyst including a support of porous structure including a zeolite-type compound and at least one photocatalytic substance present in the support, the support including channels connecting with each other, and the photocatalytic substance including metal oxide nanoparticles and being present at least at the channels of the support. 1. A structured photocatalyst comprising:a support of porous structure including a zeolite-type compound; andat least one photocatalytic substance present in the support,the support including channels connecting with each other,the photocatalytic substance being metal oxide nanoparticles and being present at least at the channels of the support,the channels include an enlarged pore portion, andthe photocatalytic substance is present at least at the enlarged pore portion.2. The structured photocatalyst according to claim 1 , whereinthe enlarged pore portion causes a plurality of pores constituting any one of a one-dimensional pore, a two-dimensional pore, and a three-dimensional pore to connect with each other.3. The structured photocatalyst according to claim 1 , whereinthe metal oxide nanoparticles include titanium or an alloy oxide including titanium.4. The structured photocatalyst according to claim 1 , whereinthe metal oxide nanoparticles have an average particle diameter that is greater than an average inner diameter of the channels and not greater than an inner diameter of the enlarged pore portion.5. The structured photocatalyst according to claim 1 , whereinthe metal oxide nanoparticles include a metal element (M) in an amount from 0.5 mass % to 2.5 mass % with respect to the structured catalyst.6. The structured photocatalyst according to claim 1 , whereinthe metal oxide nanoparticles have ...

METATHESIS CATALYSTS AND METHODS THEREOF

The present application provides, among other things, compounds and methods for metathesis reactions. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and/or stereoselectivity. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and Z-selectivity. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and E-selectivity. In some embodiments, provided technologies are particularly useful for preparing alkenyl fluorides. In some embodiments, a provided compound useful for metathesis reactions has the structure of formula II-a. In some embodiments, a provided compound useful for metathesis reactions has the structure of formula II-b. 120-. (canceled)22. The compound of claim 21 , wherein M is Mo. This application is a divisional application of U.S. patent application Ser. No. 14/933,741, filed Nov. 5, 2015, which claims priority to U.S. Provisional Application No. 62/075,315, filed Nov. 5, 2014, the entirety of each of which is incorporated herein by reference.This invention was made with government support under Grant No. GM59426 awarded by the National Institute of Health and Grant No. CHE-1362763 awarded by the National Science Foundation. The U.S. government has certain rights in the invention.The present invention generally relates to metathesis reactions.Catalytic metathesis has transformed chemical synthesis and offers exceptionally efficient pathways for the synthesis of many commercially important chemicals including biologically active molecules, oleochemicals, renewables, fine chemicals, and polymeric materials. There remains an unmet need for improved methods and catalysts for metathesis reactions, for example, in terms of better catalyst stability and/or activity, efficiency and stereoselectivity.Among other things, the present disclosure recognizes that it is particularly ...

Complexes for Nucleophilic, Radical, and Electrophilic Polyfluoroalkylation

Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions. 2. The complex of claim 1 , wherein Ris NRR.3. The complex of claim 2 , wherein Rand Rare each Calkyl.4. The complex of claim 1 , wherein Ris Calkoxy.5. The complex of claim 4 , wherein Ris methoxy.6. The complex of claim 1 , wherein Ris Calkyl.7. The complex of claim 6 , wherein Ris methyl.8. The complex of any one of - claim 6 , wherein Ris Calkyl.9. The complex of claim 1 , wherein Rand Rtaken together with the atoms to which they are attached form a 5-6-membered ring.10. The complex of claim 9 , wherein Rand Rtaken together with the atoms to which they are attached form a 5-membered ring.11. The complex of or claim 9 , wherein the ring is substituted.12. The complex of any one of to which is chiral.13. The complex of claim 10 , wherein Rand Rtaken together are —CHCHO—.14. The complex of claim 1 , wherein Ris CH claim 1 , OCH claim 1 , N(CH) claim 1 , or Rand Rtaken together are —CHCHO—.15. The complex of any one of - claim 1 , wherein Y comprises one or more F.16. The complex of any one of - claim 1 , wherein Y is Cperfluoroalkyl.17. The complex of claim 16 , wherein Y is CF claim 16 , CHF claim 16 , or CF.18. The complex of claim 16 , wherein Y is CF.19. The complex of any of - claim 16 , wherein M comprises Na claim 16 , K claim 16 , Rb claim 16 , Cs claim 16 , or NH.20. The complex of any one of - claim 16 , further comprising a crown ether.21. The complex of claim 20 , wherein the crown ether is 18-crown-6 or 15-crown-5.24. The method of claim 23 , wherein the base is KDMSO claim 23 , NaDMSO claim 23 , KOC(CH) claim 23 , KCHPh claim 23 , KH claim 23 , NaH claim 23 , or a mixture thereof.25. The method of or claim 23 , wherein the base comprises KDMSO.26. The method of or claim 23 , wherein the base comprises NaDMSO.27. The method of any one of - claim 23 , wherein Ris NRR.28. The method of claim 27 , wherein Rand Rare each Calkyl.29. The method of any one of - claim ...

TRI-(ADAMANTYL)PHOSPHINES AND APPLICATIONS THEREOF

In one aspect, phosphine compounds comprising three adamantyl moieties (PAd) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAdligands are also provided for catalytic synthesis including catalytic cross-coupling reactions. 1. A method of synthesizing a tri-(adamantyl)phosphine compound , PAd , comprising:{'sub': 2', '2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphine (PAd) and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}2. The method of claim 1 , wherein adamantyl moieties (Ad) of the PAdare independently selected from the group consisting of adamantane claim 1 , diamantane claim 1 , triamantane and derivatives thereof.3. The method of claim 1 , wherein the substituted adamantyl moiety comprises a leaving group.4. The method of claim 3 , wherein the leaving group is selected from the group consisting of acetate claim 3 , triflate claim 3 , tosylate and hydroxyl.5. The method of claim 1 , wherein yield of the PAdis greater than 50 percent.6. The method of claim 1 , wherein yield of the PAdis greater than 60 percent.7. The method of claim 1 , wherein synthesizing the tri-(adamantyl)phosphine is performed at room temperature.8. A method of synthesizing a tri-(adamantyl)phosphine compound claim 1 , PAd claim 1 , comprising:{'sub': 2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphide and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}9. The method of claim 8 , wherein adamantyl moieties (Ad) of the di-(adamantyl)phosphide are independently selected from the group consisting of ...

SPIRO-1,1'-BINDANE-7,7-BISPHOSPHINE OXIDES AS HIGHLY ACTIVE SUPPORTING LIGANDS FOR PALADIUM-CATALYZED ASYMMETRIC HECK REACTION

The present invention relates to catalyst complexes comprising palladium (Pd) and at least one spiro-1,1′-biindane-7,7′-bisphosphine oxide ligand as disclosed herein, and their use. The present invention is further directed to the asymmetric catalyzed covalent carbon-carbon single bond formation from aryl, heteroaryl and alkenyl triflates and halides and olefins utilising the said catalyst complexes.

Complexes

The present invention provides a palladium(II) complex of formula (1). 2. A palladium(II) complex according to claim 1 , wherein Ris selected from the group consisting of substituted and unsubstituted straight-chain alkyl claim 1 , substituted and unsubstituted branched-chain alkyl claim 1 , substituted and unsubstituted cycloalkyl claim 1 , substituted and unsubstituted aryl claim 1 , and substituted and unsubstituted heteroaryl wherein the heteroatoms are independently selected from sulfur claim 1 , nitrogen and oxygen.3. A palladium(II) complex according to claim 1 , wherein X is a halo group or a trifluoroacetate group.6. A process for carrying out a carbon-carbon coupling reaction or a carbon-heteroatom coupling reaction in the presence of a catalyst claim 1 , the process comprising the use of a complex of formula (1) as defined in .7. The process of claim 6 , wherein the carbon-carbon coupling reaction is (a) a Heck reaction; (b) a Suzuki reaction; (c) a Sonogashira reaction; or (d) a Negishi reaction and the carbon-heteroatom coupling reaction is a Buchwald-Hartwig amination reaction. This application is a divisional of U.S. patent application Ser. No. 16/686,960, filed Nov. 18, 2019, which is a divisional of U.S. patent application Ser. No. 16/284,841, filed Feb. 25, 2019, now U.S. Pat. No. 10,858,382, which is a divisional of U.S. patent application Ser. No. 15/318,106, filed Dec. 12, 2016, now U.S. Pat. No. 10,253,056, which is a US national stage of International patent Application No. PCT/GB2015/050835, filed Mar. 20, 2015, which claims priority to U.S. Provisional Patent Application No. 62/011,168, filed Jun. 12, 2014, all applications of which are incorporated by reference herein.The present invention relates to optionally substituted π-allyl palladium complexes and their use thereof in coupling reactions.WO2011/161451 (to Johnson Matthey PLC) describes π-allyl complexes, such as π-allyl palladium complexes and π-allyl nickel complexes.Faller et al ( ...

METHODS FOR ENANTIOSELECTIVE ALLYLIC ALKYLATION OF ESTERS, LACTONES, AND LACTAMS WITH UNACTIVATED ALLYLIC ALCOHOLS

The present disclosure provides methods for enantioselective synthesis of cyclic and acyclic α-quaternary carboxylic acid derivatives via nickel-catalyzed allylic alkylation. 2. The method of claim 1 , wherein:X is O;{'sub': '1', 'Ris ethyl;'}{'sub': '2', 'Ris H;'}the organic solvent is toluene, diethyl ether, MTBE, THF, or dioxane; andthe reaction temperature is 0° C., −10° C., or 23° C.3. The method of claim 2 , wherein Rand Rare each H and the organic solvent is diethyl ether.4. The method of claim 3 , wherein 10 mol % Ni(COD)and 12 mol % of ligand are used.5. The method of claim 3 , wherein the reaction temperature is 0° C. claim 3 , the ligand is (R)-P-phos claim 3 , and 5 mol % Ni(COD)and 6 mol % of ligand are used.6. The method of claim 2 , wherein:{'sub': 8', '9, 'Rand Rare each H;'}{'sub': '2', '10 mol % Ni(COD)and 12 mol % of ligand are used;'}the reaction temperature is 23° C.; andthe organic solvent is toluene, MTBE, THF, or dioxane.7. The method of claim 1 , wherein:X is O;the compound of Formula (II) is a compound of Formula (IIb);{'sub': '2', '10 mol % of Ni(COD)and 12 mol % of L are used;'}L is (R)-P-phos; andthe organic solvent is diethyl ether.8. The method of claim 7 , wherein{'sub': '2', 'Ris H;'}{'sub': 8', '9, 'Rand Rare each H; and'}the reaction temperature is −10° C.9. The method of claim 7 , wherein{'sub': '1', 'Ris ethyl;'}{'sub': '2', 'Ris H;'}{'sub': 8', '9', '8', '9, 'Rand Rcombine to form a phenyl ring including the carbon atoms to which Rand Rare attached; and'}the reaction temperature is −10° C.10. The method of claim 7 , wherein{'sub': '1', 'Ris ethyl;'}{'sub': '2', 'Ris Ph, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-trifluoromethylphenyl, 3,5-dimethylphenyl, 2-naphthyl, 2-methoxyphenyl, 2-furyl, 2-thienyl, methyl, or styryl;'}{'sub': 8', '9, 'Rand Rare each H; and'}the reaction temperature is 10° C.11. The method of claim 1 , wherein X is N-PG claim 1 , PG is benzoyl claim 1 , Ris ethyl claim 1 , Ris H claim ...

Precatalyst for shibasaki's rare earth metal binolate catalysts

Disclosed herein are schemes for the synthesis of novel hydrogen-bonded rare earth-BINOLate precatalyst complexes, the precatalysts, per se, and their application for the generation of anhydrous REMB catalysts by cation-exchange from metal halides.

General method for functionalizing carbon nanotubes via solvent free diels-alder reactions

The present invention provides methods by which carbon nanotubes can be functionalized via Diels-Alder reactions under solvent free conditions. Such methods include reacting carbon nanotubes with Diels-Alder dienes or dienophiles to obtain adducts that includes the diene or dienophile moiety bound to the carbon nanotubes. Functionalized carbon nanotubes and dispersions containing functionalized carbon nanotubes are provided. The present invention provides functionalization methods of carbon nanotubes through gas phase, liquid phase, or solid phase reactions without any solvents other than the reactants. Such processes are also amenable to a wide variety of chemical reactions that use other functionalizing agents. Additionally, such methods are cost effective, easily scalable and can provide for functionalized CNTs in large, industrial-scale quantities.

Complex and structurally diverse compounds

The invention provides a novel, general, and facile strategy for the creation of small molecules with high structural and stereochemical complexity. Aspects of the methods include ring system distortion reactions that are systematically applied to rapidly convert readily available natural products to structurally complex compounds with diverse molecular architectures. Through evaluation of chemical properties including fraction of sp 3 carbons, ClogP, and the number of stereogenic centers, these compounds are shown to be significantly more complex and diverse than those in standard screening collections. This approach is demonstrated with natural products (gibberellic acid, adrenosterone, and quinine) from three different structural classes, and methods are described for the application of this strategy to any suitable natural product.

Method For Preparation of Alkylated or Fluoro, Chloro and Fluorochloro Alkylated Compounds By Heterogeneous Catalysis

The invention discloses a method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by a heterogeneous Pt/C-catalyzed alkylation or fluoro, chloro and fluorochloro alkylation with alkyl halides or with fluoro, chloro and fluorochloro alkyl halides in the presence of CsC0or CsHC0. 116-. (canceled)19. The method according to claim 17 , whereinm, n and q are identical or different and independently from each other 0, 1, 2, 3 or 4.21. The method according to claim 17 , whereinX is Br or I.22. The method according to claim 17 , whereinX is I.23. The method according to claim 17 , wherein{'sub': 2', '2, 'compound FCLALKYLHADLIDE is a perfluoroalkyl halide, FHC—Cl or FHC—Br.'}24. The method according to claim 17 , whereinX is Cl, Br or I, and{'sub': '1-20', 'R3 is perfluoro Calkyl; or'}{'sub': 2', '2, 'FCLALKYLHADLIDE is FHC—Cl or FHC—Br.'}25. The method according to claim 17 , wherein{'sub': 21', '10', '17', '8', '13', '6', '9', '4', '3', '3', '3', '2', '2, 'FCLALKYLHALIDE is selected from the group consisting of FC—I, FC—I, FC—I, FC—I, FC—I, FC—Br, FC—Cl, FHC—Cl and FHC—Br.'}26. The method according to claim 17 , whereinthe reaction is done in the presence of a compound COMPSALT;wherein COMPSALT is selected from the group consisting of NaI, KI, CsI and N(R30)(R31)(R32)R33I; and{'sub': '1-10', 'R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and Calkyl.'}27. The method according to claim 26 , wherein{'sub': '2-6', 'R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and Calkyl.'}28. The method according to claim 26 , wherein{'sub': '4', 'COMPSALT is selected from the group consisting of NaI and (n-Bu)NI.'}29. The method according to claim 17 , whereinthe amount of Pt in CAT is from 0.1 to 20%, the % are % by weight and are based on the combined weight of Pt and C in CAT.30. The method according ...

ORGANIC REACTIONS CARRIED OUT IN AQUEOUS SOLUTION IN THE PRESENCE OF A HYDROXYALKYL(ALKYL)CELLULOSE OR AN ALKYLCELLULOSE

The present invention relates to a method of carrying out an organic reaction in aqueous solution in the presence of a hydroxyalkyl(alkyl)cellulose or an alkylcellulose. 1. A method of carrying out an organic reaction in a solvent containing at least 90% by weight , in particular at least 97% by weight , based on the total weight of the solvent , of water , which method comprises reacting the reagents in said solvent in the presence of a cellulose derivative which is selected from the group consisting of cellulose modified with one or more alkylene oxides or other hydroxyalkyl precursors , and alkylcellulose;where the organic reaction is not a polymerization or oligomerization reaction of olefinically unsaturated compounds.2. The method as claimed in claim 1 , where the cellulose derivative has a viscosity of from 1 to 150000 mPa·s claim 1 , in particular 2 to 100000 mPa·s claim 1 , specifically 2 to 10000 mPa·s claim 1 , determined as a 2% by weight aqueous solution claim 1 , relative to the weight of water.3. The method as claimed in claim 1 , where in the cellulose derivative 5 to 70% claim 1 , in particular 10 to 60% claim 1 , especially 15 to 50% of the hydrogen atoms in the hydroxyl groups of the cellulose on which the cellulose derivative is based are replaced by a hydroxyalkyl and/or alkyl group.4. The method as claimed in claim 1 , where the cellulose modified with one or more alkylene oxides or other hydroxyalkyl precursors is selected from the group consisting of hydroxyalkylcelluloses which are celluloses in which a part of the hydrogen atoms of the OH groups is replaced by a C-C-hydroxyalkyl group; hydroxyalkylalkylcelluloses which are celluloses in which a part of the hydrogen atoms of the OH groups is replaced by a C-C-hydroxyalkyl group and a part of the hydrogen atoms of the OH groups is replaced by a C-C-alkyl group; and alkylcelluloses which are celluloses in which a part of the hydrogen atoms of the OH groups is replaced by a C-C-alkyl group.5. ...

METHODS AND SYSTEMS FOR OPTIMIZING MECHANICAL VAPOR COMPRESSION AND/OR THERMAL VAPOR COMPRESSION WITHIN MULTIPLE-STAGE PROCESSES

The present invention utilizes mechanical vapor compression and/or thermal vapor compression integrating compression loops across multiple process stages. A sequential network of compressors is utilized to increase the pressure and condensing temperature of the vapors within each process stage, as intra-vapor flow, and branching between process stages, as inter-vapor flow. Because the vapors available are shared among and between compressor stages, the number of compressors can be reduced, improving economics. Balancing vapor mass flow through incremental compressor stages which traverse multiple process stages by splitting vapors between compressor stages enables the overall vapor-compression system to be tailored to individual process energy requirements and to accommodate dynamic fluctuations in process conditions. 1. A multiple-stage , energy-integrated system comprising:(a) a plurality of process sub-systems collectively configured for continuously or semi-continuously converting a feedstock into one or more products, wherein said plurality of process sub-systems is configured to utilize vapor-liquid phase changes; and(b) a vapor-compression sub-system, wherein said vapor-compression sub-system includes at least a first vapor compressor and a second vapor compressor, wherein said first vapor compressor is a mechanical vapor compressor or a thermal vapor compressor, and wherein said second vapor compressor is a mechanical vapor compressor or a thermal vapor compressor,wherein said first and second vapor compressors are sequentially arranged and configured to increase pressure and condensing temperature of first vapors within a first process sub-system and second vapors within a second process sub-system that is physically separated from, but in flow communication with, said first process sub-system;wherein said first vapor compressor is in flow communication with said second process sub-system, or a third process sub-system, via a first compressed-vapor line, ...

Method for purification of substances contaminated with organic chemicals

The present invention provides a method for purifying organic chemical-containing contaminated substances by which various organic chemicals (contaminants) can be readily and sufficiently decomposed in a short time, the method comprising the steps of adding a metal salt and a transition metal ionic compound to water or soil that contains organic chemicals, decomposing the organic chemicals by irradiating with light, and separating/collecting the detoxified organic chemicals.

METHODS OF PREPARING OXA-BICYCLOALKENE

Disclosed is a method of preparing an oxa-bicycloalkene via the reaction of a cycloalkanone and an allyl alcohol compound in the presence of an organic acid, a manganese catalyst, and oxygen at a predetermined temperature. 1. A method of preparing an oxa-bicycloalkene comprising reacting (i) a cycloalkanone and (ii) an allyl alcohol compound in the presence of an organic acid , a manganese catalyst , and oxygen at a temperature of 60 to 200° C. for 1 to 24 hours.2. The method of claim 1 , wherein the cycloalkanone has 4 to 16 ring atoms selected from carbon claim 1 , oxygen claim 1 , sulfur claim 1 , and nitrogen; the allyl alcohol compound is allyl alcohol or an ester claim 1 , ether claim 1 , oxime claim 1 , or silyl of allyl alcohol; the organic acid is acetic acid claim 1 , and the manganese catalyst is a manganese (II) compound selected from the group consisting of manganese (II) acetate claim 1 , manganese (II) sulfate claim 1 , manganese (II) chloride claim 1 , manganese (II) bromide claim 1 , manganese (II) iodide claim 1 , manganese (II) oxide claim 1 , manganese (II) triflate claim 1 , and manganese (II) perchlorate.3. The method of claim 2 , wherein the allyl alcohol compound is allyl alcohol or allyl acetate claim 2 , and the manganese catalyst is supported on a zeolite claim 2 , aluminophosphate claim 2 , polyoxometallate claim 2 , or combination thereof.4. The method of claim 1 , wherein the molar ratio between the cycloalkanone and the allyl alcohol compound is 20:1 to 1:6 claim 1 , the molar ratio between the organic acid and the allyl alcohol is 100:1 to 1:1 claim 1 , and the molar ratio between the manganese catalyst and the allyl alcohol is 1:1000 to 1:1.5. The method of claim 1 , wherein the reaction is performed in the presence of peracetic acid claim 1 , the molar ratio between the peracetic acid and the allyl alcohol compound is 1:1 to 100:1 claim 1 , and the peracetic acid is added to the reaction or generated in-situ from the reaction of ...

METHOD FOR COUPLING A FIRST AROMATIC COMPOUND TO A SECOND AROMATIC COMPOUND

In one aspect, there is provided a method of coupling a first aromatic compound having a fluorosulfonate substituent to a second aromatic compound having a boron-containing substituent. In another aspect, there is provided a method of coupling a first aromatic compound having a hydroxyl substituent to a second aromatic compound having a boron-containing substituent in a one-pot reaction. 1. A method of coupling a first aromatic compound to a second aromatic compound , the method comprising:providing the first aromatic compound having a fluorosulfonate substituent; 'reacting the first aromatic compound and the second aromatic compound in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first aromatic compound to the second aromatic compound.', 'providing the second aromatic compound having a boron-containing substituent; and'}2. The method of claim 1 , wherein the reaction mixture further includes a ligand claim 1 , and a base.3. The method of claim 1 , wherein at least one of the first aromatic compound or the second aromatic compound is heteroaryl.4. The method of wherein the catalyst is a palladium catalyst or a nickel catalyst.5. The method of claim 4 , wherein the catalyst is generated in-situ from a palladium precatalyst claim 4 , the palladium precatalyst is selected from the group consisting of: Palladium(II) acetate claim 4 , Palladium(II) chloride claim 4 , Dichlorobis(acetonitrile)palladium(II) claim 4 , Dichlorobis(benzonitrile)palladium(II) claim 4 , Allylpalladium chloride dimer claim 4 , Palladium(II) acetylacetonate claim 4 , Palladium(II) bromide claim 4 , Bis(dibenzylideneacetone)palladium(0) claim 4 , Bis(2-methylallyl)palladium chloride dimer claim 4 , Crotylpalladium chloride dimer claim 4 , Dichloro(1 claim 4 ,5-cyclooctadiene)palladium(II) claim 4 , Dichloro(norbornadiene)palladium(II) claim 4 , Palladium(II) trifluoroacetate claim 4 , ...

HERBAL DECARBOXYLATION AND INFUSION SYSTEM

A system for decarboxylating and infusing an organic material includes a decarboxylation and infusion apparatus is provided. The apparatus includes a heated reservoir in operable communication with a user interface whereon a user selects decarboxylation and infusion settings. The heated reservoir has a mixing element to agitate an organic material and solvent disposed therein as well as a filter to filter the organic material following the infusion. 1. A system for decarboxylating and infusing an organic material , the system comprising:a decarboxylation and infusion apparatus including a heated reservoir in operable communication with a user interface whereon a user selects decarboxylation and infusion settings, the heated reservoir including a mixing element to agitate an organic material and solvent disposed therein; anda fan to actively cool the heated reservoir, the fan in communication with a vent having a filter, the vent to expel and deodorize air emitted therefrom.2. The system of claim 1 , wherein the user interface is provided on a smart device in wireless communication with the decarboxylation and infusion apparatus.3. The system of claim 1 , wherein infusion setting is comprised of a time setting and a temperature setting.4. The system of claim 1 , wherein the solvent is comprised of at least one of the following: an oil claim 1 , a butter claim 1 , an alcohol claim 1 , or a glycerin.5. The system of claim 1 , wherein a user performs the steps of:disposing an amount of the organic materials into the reservoir of the decarboxylation and infusion apparatus;sealing the reservoir;selecting a decarboxylation option via the user interface;selecting a start option via the user interface;decarboxylating, via the decarboxylation and infusion apparatus, the organic material;opening the reservoir and providing an amount of the solvent to the reservoir;sealing the reservoir and selecting an infusion setting via the user interface;infusing, via the decarboxylation ...

Ylide-functionalised phosphanes for use in metal complexes and homogeneous catalysis

The invention relates to ylide-functionalized phosphane ligands, the production of same and use in transition metal compounds, as well as the use of same as catalysts in organic reactions.

IONIC METAL ALKYLIDENE COMPOUNDS AND USE THEREOF IN OLEFINIC METATHESIS REACTIONS

A compound of formula (I) wherein: M is selected from Mo or W; X is selected from O or NR; Rand Rare independently selected from H, Calkyl, and aryl; Calkyl and aryl optionally being substituted with one or more of Calkyl, Calkoxy, and O—CH; Ris selected from a nitrogen-containing aromatic heterocycle being bound to M via said nitrogen; and from halogen; Ris an aryl oxy group being bound to M via said oxygen of said aryl oxy group; wherein said aryl group Ar of said aryl oxy group is bound to a group Cat such to form a cationic ligand Cat-Z—ArO—, wherein Z is either a covalent bond or a linker; Ris alkyl or aryl, optionally substituted. 2. The compound of claim 1 , wherein Rand Rare independently selected from H claim 1 , C(CH) claim 1 , C(CH)CH claim 1 , and phenyl substituted in o-position with Calkoxy.3. The compound of claim 1 , wherein Ris selected from pyrrol-1-yl claim 1 , pyrazol-1-yl claim 1 , imidazol-1-yl claim 1 , 1H-1 claim 1 ,2 claim 1 ,3-triazol-1-yl claim 1 , 2H-1 claim 1 ,2 claim 1 ,3-triazol-2-yl claim 1 , 1H-1 claim 1 ,2 claim 1 ,4-triazol-1-yl claim 1 , 4H-1 claim 1 ,2 claim 1 ,4-triazo-4-yl claim 1 , indol-1-yl claim 1 , indazol-1-yl claim 1 , and azaindol-1-yl claim 1 , optionally substituted with one or more substituents selected independently from Calkyl claim 1 , Calkoxy claim 1 , phenyl claim 1 , halogen claim 1 , or cyano claim 1 , preferably pyrrol-1-yl claim 1 , 2 claim 1 ,5-dimethylpyrrol-1-yl claim 1 , and 2 claim 1 ,5-diphenylpyrrol-1-yl or indol-1-yl or a substituted indol-1-yl.4. The compound of claim 1 , wherein Ris selected from halogen.5. The compound of claim 1 , wherein said Ar in said Cat-Z—ArO— is phenyl substituted in 2 claim 1 ,6-position with phenyl claim 1 , optionally substituted claim 1 , or with isopropyl or t-butyl claim 1 , respectively; or{'sup': +', '+, 'said Ar in Cat-Z—ArO— is phenyl substituted in 4-position with Cat-Z—; or'}{'sup': '+', 'said Ar in Cat-Z—ArO— is phenyl substituted in 2,6 position with phenyl, ...

SELECTIVE OLEFIN METATHESIS WITH CYCLOMETALATED RUTHENIUM COMPLEXES

This invention relates generally to C—H activated ruthenium olefin metathesis catalyst compounds which are stereogenic at the ruthenium center, to their preparation, and the use of such catalysts in the metathesis of olefins and olefin compounds. In particular, the invention relates to the use of C—H activated ruthenium olefin metathesis catalyst compounds in Z-selective olefin metathesis reactions, enantio-selective olefin metathesis reactions, and enantio-Z-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry. 2. The olefin metathesis catalyst complex claim 1 , according to claim 1 , wherein:{'sup': '1', 'sub': 1', '6', '1', '6, 'Ris C-Calkyl, C-Calkoxy, or halide;'}{'sup': '2', 'sub': 2', '6', '1', '6', '2', '2', '3', '5', '8', '5', '8', '1', '6', '1', '6, 'Ris C-Calkyl, substituted C-Calkyl, (e.g., CFH, CFH, CF, etc.), C-Ccycloalkyl, C-Csubstituted cycloalkyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, where the substituents are selected from C-Calkyl, C-Calkoxy, or halide;'}{'sup': 4', '5', '6', '7', '8, 'R, R, R, Rand Rare independently hydrogen;'}Y is O;{'sub': 1', '6, 'Z is C-Calkyl;'}n is 1; and{'sup': 1', '−, 'sub': 3', '2, 'Xis NO or t-BuCO.'}3. The olefin metathesis catalyst complex claim 2 , according to claim 2 , wherein:{'sup': '1', 'Ris Me, OMe or F;'}{'sup': '2', 'sub': '3', 'Ris MeO, iPr, Me, F, or CF; and'}Z is i-Pr.4. The olefin metathesis catalyst complex claim 2 , according to claim 2 , wherein:{'sup': '1', 'Ris Me, OMe, or F;'}{'sup': '2', 'sub': '3', 'Ris MeO, Me, iPr, or CF;'}Z is i-Pr; and{'sup': 1', '−, 'sub': '3', 'Xis NO.'}5. The olefin metathesis catalyst complex claim 2 , according to claim 2 , wherein:{'sup': '1', 'Ris MeO, Me or F;'}{'sup': '2', 'sub': '3', 'Ris MeO, iPr, Me or CF;'}Z is i-Pr; and{'sup': '1', 'sub': '2', 'Xis t-BuCO.'}7. A method for performing an enantio- ...

SYNTHESIS OF A COMPOUND THAT MODULATES THE ACTIVITY OF BROMODOMAIN-CONTAINING PROTEINS

The present disclosure provides processes for the preparation of a compound of formula I: 2. The process of claim 1 , wherein the process comprises a base.3. The process of claim 2 , wherein the base is a carbonate claim 2 , bicarbonate claim 2 , acetate or phosphate.4. The process of claim 3 , wherein the base is potassium carbonate claim 3 , sodium carbonate claim 3 , cesium carbonate claim 3 , potassium bicarbonate claim 3 , sodium bicarbonate claim 3 , sodium acetate claim 3 , potassium acetate claim 3 , a dibasic phosphate or a tribasic phosphate.5. The process of claim 4 , wherein the base is sodium carbonate.6. The process of claim 1 , wherein the process comprises a Pd(0) or a Pd(II) catalyst.7. The process of claim 1 , wherein the process comprises a solvent selected from tetrahydrofuran claim 1 , 2-methyltetrahydrofuran claim 1 , n-propanol claim 1 , toluene claim 1 , N claim 1 ,N-dimethylformamide claim 1 , N claim 1 ,N-dimethylacetamide claim 1 , dimethoxyethane claim 1 , isopropyl acetate claim 1 , n-butanol claim 1 , t-amyl alcohol claim 1 , methanol claim 1 , ethanol claim 1 , isopropanol claim 1 , acetone claim 1 , methyl ethyl ketone claim 1 , ethyl acetate claim 1 , and N-methyl-2-pyrrolidone claim 1 , or a combination thereof with water.8. The process of claim 7 , wherein the solvent is 2-methyltetrahydrofuran and water.9. The process of claim 1 , wherein the process comprises a temperature from about 40° C. to about 100° C.10. The process of claim 9 , wherein the temperature is from about 55° C. to about 65° C.12. The process of claim 11 , wherein step (a) comprises a solvent selected from a Calcohol or a mixture thereof13. The process of claim 11 , wherein step (a) comprises a temperature from about 20° C. to about 65° C.14. The process of claim 11 , wherein step (a) comprises methanol as a solvent and a temperature from about 45° C. to about 55° C.15. The process of claim 11 , wherein step (b) comprises a base.16. The process of claim 15 , ...

METHOD FOR DECARBOXYLATION OF AMINO ACIDS VIA IMINE FORMATION

The present application provides methods for decarboxylation of amino acids via imine formation with a catalyst under superheated conditions in either a microwave or oil bath. 1. A method for decarboxylation of amino acids , the method comprising:combining, in a pressurized reaction vessel, a mixture of an amino acid, a solvent, and a catalyst; andheating the mixture at about 180° C., or more, for about 5 minutes, or more, wherein the solvent has a lower boiling point than cyclohexanol and does not produce a maximum vapor pressure exceeding the vessel limit,wherein the amino acid is converted to its imine.2. The method of claim 1 , wherein the solvent is a short chain alcohol or water.3. The method of claim 1 , wherein the solvent is selected from the group consisting of: water claim 1 , n-butanol claim 1 , n-pentanol claim 1 , isopropanol claim 1 , ethanol claim 1 , methanol claim 1 , and n-propanol.4. The method of claim 1 , wherein the solvent is n-propanol.5. The method of claim 1 , wherein the catalyst is selected from the group consisting of: ceyclohex-2-ene-1-one claim 1 , acetophenone claim 1 , R-carvone claim 1 , S-carvone claim 1 , and acetone.6. The method of claim 1 , wherein the catalyst is R-carvone.7. The method of when the amount of catalyst is from about 0.1 to about 2 mole equivalents.8. The method of claim 1 , wherein mixture is heated in a microwave to a temperature of about 180° C. to about 190° C. and maintained at a temperature of about 180° C. to about 190° C. for about 5 min to about 10 min.9. The method of claim 8 , wherein the mixture is heated in a microwave to a temperature of about 190° C. for about 5 min claim 8 , and if the reaction mixture is not clear after the 5 minutes of heating claim 8 , the mixture is heated in the microwave to about 190° C. for about 5 to about 25 min longer.10. The method of claim 1 , wherein the mixture is heated in an oil bath at a temperature of about 180° C. to about 190° C. for about 5 min to about 20 ...

Rapid Thermal Isomerization of Lycopene

The use of lycopene has been demonstrated to be effective in decreasing risk factors associated with cardiovascular disease, skin cancer and prostate cancer in mammals. Lycopene is difficult to solubilize in its native trans-lycopene form. Cis-lycopene, formed by applying thermal energy generated by excitation of polar molecules through microwave-assisted processing, appears in several isomeric forms. The cis isomers are effective in improving lycopene micellularization, bioaccessibility and mammalian absorption. The cis isomers are effective in improving vascular circulation of lycopene by way transport vesicle low density lipo-protein (LDL). Lycopene-based ingredients, end products, functional foods, medical foods and nutraceuticals, containing isomerized cis-lycopene can be used in place of ingredients with more naturally abundant trans-lycopene as phytonutrient, micronutrient and antioxidant delivery vehicles through dietary consumption to improve the outcomes of a variety of conditions, including hypertension, cardiovascular disease, skin cancer, prostate cancer, macular degeneration and related proinflammatory conditions. 1. A process for the rapid thermal isomerization of a mixture of all-trans-lycopene and its cis-isomers of any composition to increase the proportion of cis-isomers , wherein the isomerization takes place in a polar solvent.2. A functional ingredient , nutraceutical , functional food , medical food composition suitable for administration to mammal , comprising greater than 4% of isomerized cis-lycopene compared to total lycopene content.3. A process claimed in claim 1 , wherein the isomerization takes place by way of energizing polar water molecules and ionic salt compounds through friction within the food mixture matrix using microwave-assisted heating4. A process claimed in claim 1 , wherein the isomerization takes place by way of energizing food mixture matrix using volumetric heating.5. A process as claimed in claim 1 , wherein the ...

ETHYLENE-TO-LIQUIDS SYSTEMS AND METHODS

The present disclosure provides petrochemical processing methods and systems, including ethylene conversion processes and systems, for the production of higher hydrocarbon compositions, for example liquid hydrocarbon compounds, with reduced amount of unsaturated hydrocarbons. 171.-. (canceled)72. A method for generating oxygenate compounds with five or more carbon atoms (Coxygenates) , comprising:{'sub': 2', '4', '2', '4', '5+, '(a) directing an unsaturated hydrocarbon feed stream comprising ethylene (CH) into an ethylene-to-liquids (ETL) reactor that converts said CHin an ETL process to yield a product stream comprising compounds with five or more carbon atoms (Ccompounds); and'}{'sub': 5+', '5+, '(b) directing at least a portion of said product stream from said ETL reactor into a hydration unit that reacts said Ccompounds in said at least said portion of said product stream in a hydration process to yield an oxygenate product stream comprising said Coxygenates.'}73. The method of claim 72 , wherein said Ccompounds comprise olefins claim 72 , and wherein said method further comprises converting said olefins to said oxygenate product stream comprising said Coxygenates.74. The method of claim 72 , wherein subsequent to (b) claim 72 , said product stream comprises at most about 10 wt % olefins.75. The method of claim 72 , wherein said hydration unit comprises a hydration catalyst that facilitates a hydration reaction in said hydration process.76. The method of claim 75 , wherein said hydration catalyst comprises an acid catalyst selected from the group consisting of water soluble acids claim 75 , organic acids claim 75 , metal organic frameworks (MOF) claim 75 , and solid acids.77. The method of claim 72 , wherein (b) further comprises directing water into said hydration reactor claim 72 , wherein said water reacts with said Ccompounds in said hydration process to yield said Coxygenates.78. The method of claim 77 , wherein a molar ratio of said water to said ...

Carbon Dioxide as a Directing Group for C-H Functionalization Reactions Involving Lewis Basic Amines, Alcohols, Thiols, and Phosphines for the Synthesis of Compounds

Methods of synthesizing compounds using COas a directing group for C—H functionalization, and compounds made thereby, are described. 1. A method of functionalizing a C—H bond , the method comprising using COas a directing group to convert a C—H bond in a substrate compound into a C—C , C—B , C—N , C—O , C—F , C—Cl , C—Br , C—I , C—P , or C—S bond , wherein the substrate compound comprises an amine , alcohol , thiol , or phosphine functional group.2. The method of claim 1 , wherein the C—H bond is in a γ-position relative to the amine claim 1 , alcohol claim 1 , thiol claim 1 , or phosphine functional group.3. The method of claim 1 , wherein the substrate compound is reacted with a reactant in the presence of COand a transition metal catalyst.4. The method of claim 3 , wherein the transition metal catalyst comprises palladium.5. The method of claim 1 , wherein the amine is a primary amine.6. The method of claim 5 , wherein the primary amine is selected from the group consisting of: 1-ethylcyclopentan-1-amine (S-1) claim 5 , 1-ethylcyclohexan-1-amine (S-2) claim 5 , 1-ethylcycloheptan-1-amine (S-3) claim 5 , 4-(tert-butyl)-1-ethylcyclohexan-1-amine (S-4) claim 5 , 9-ethyl-9H-fluoren-9-amine (S-5) claim 5 , 3-methylheptan-3-amine (S-6) claim 5 , 3-methylnon-3-amine (S-7) claim 5 , 3-methylpentan-3-amine (S-8) claim 5 , 3-ethylpentan-3-amine (S-9) claim 5 , and heptan-3-amine (S-10).7. The method of claim 1 , wherein the amine is a secondary amine.8. The method of claim 7 , wherein the secondary amine is selected from the group consisting of: N-(tert-pentyl)propan-1-amine (S-12) claim 7 , N-(tert-pentyl)butan-1-amine (S-13) claim 7 , N-(tert-pentyl)pentan-1-amine (S-14) claim 7 , 2-methyl-N-phenethylbutan-2-amine (S-15) claim 7 , N-benzyl-2-methylbutan-2-amine (S-16) claim 7 , N-(4-methoxybenzyl)-2-methylbutan-2-amine (S-17) claim 7 , N-(3-methoxybenzyl)-2-methylbutan-2-amine (S-18) claim 7 , N-(4-tolyl)-2-methylbutan-2-amine (S-19) claim 7 , N-(3-tolyl)-2-methylbutan-2 ...

Silicon-based cross coupling agents and methods of their use

Compositions and methods using silicon-based cross-coupling agents in the formation of carbon-carbon and carbon-nitrogen bonds are described.

NOVEL SUGAR DERIVATIVE GELATORS

A novel gelator including a sugar derivative; a gelator including a compound of Formula (1) or Formula (2): 4. A gel comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'the gelator as claimed in ; and'}a hydrophobic organic solvent, a hydrophilic organic solution, a hydrophobic organic solution, or an aqueous solution.5. A gel comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'the gelator as claimed in ;'}a surfactant; anda hydrophobic organic solvent, a hydrophilic organic solvent, water, a hydrophilic organic solution, a hydrophobic organic solution, or an aqueous solution.6. The gel according to claim 4 , wherein the hydrophobic organic solvent is at least one solvent selected from the group consisting of vegetable oils claim 4 , esters claim 4 , silicone oils claim 4 , and hydrocarbons.7. The gel according to claim 4 , wherein the hydrophobic organic solution is a mixed solvent of water and the hydrophobic organic solvent wherein the hydrophobic organic solvent is at least one solvent selected from the group consisting of vegetable oils claim 4 , esters claim 4 , silicone oils claim 4 , and hydrocarbons.8. The gel according to claim 5 , wherein the hydrophilic organic solvent is at least one solvent selected from the group consisting of methanol claim 5 , ethanol claim 5 , 2-propanol claim 5 , i-butanol claim 5 , pentanol claim 5 , hexanol claim 5 , 1-octanol claim 5 , iso-octanol claim 5 , acetone claim 5 , cyclohexanone claim 5 , acetonitrile claim 5 , dioxane claim 5 , glycerol claim 5 , propylene glycol claim 5 , ethylene glycol claim 5 , and dimethyl sulfoxide.9. The gel according to claim 4 , wherein the hydrophilic organic solution is a mixed solvent of water and the hydrophilic organic solvent wherein the hydrophilic organic solvent is at least one solvent selected from the group consisting of methanol claim 4 , ethanol claim 4 , 2-propanol claim 4 , i-butanol claim 4 , pentanol claim 4 , hexanol claim 4 , 1-octanol claim 4 , iso- ...

Iron bisphenolate complexes and methods of use and synthesis thereof

The present application, relates to iron bisphenolate complexes and methods of use and synthesis thereof. The iron complexes are prepared from tridentate or tetradentate ligands of Formula I: wherein R 1 and R 2 are as defined herein. Also provided are methods and processes of using the iron bisphenolate complexes as catalysts in cross-coupling reactions and in controlled radical polymerizations.

Conversion of glucose to sorbose

The present invention is directed to methods for preparing sorbose from glucose, said method comprising: (a) contacting the glucose with a silica-containing structure comprising a zeolite having a topology of a 12 membered-ring or larger, an ordered mesoporous silica material, or an amorphous silica, said structure containing Lewis acidic Ti 4+ or Zr 4+ or both Ti 4+ and Zr 4+ framework centers, said contacting conducted under reaction conditions sufficient to isomerize the glucose to sorbose. The sorbose may be (b) separated or isolated; or (c) converted to ascorbic acid.

Process for Preparing Substituted Biphenyls

The present invention relates to a process for preparing substituted biphenyls via Suzuki coupling using specific phosphorus ligands and a solvent mixture containing water, a non-polar organic solvent and a polar aprotic co-solvent. 120-. (canceled)22. The process of claim 21 , wherein Ris nitro.23. The process of claim 21 , wherein Ris fluorine or chlorine claim 21 , and n is 1 claim 21 , 2 or 3.24. The process of claim 21 , wherein Ris hydrogen or fluorine.25. The process of claim 21 , wherein Rand Rare in para positions to one another.26. The process of claim 21 , wherein the biphenyl I is 4-chloro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4-dichloro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4-difluoro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4 claim 21 ,5-trifluoro-2′-nitro-biphenyl claim 21 , 3-chloro-4 claim 21 ,5-difluoro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4-dichloro-5′-fluoro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,5-dichloro-4-fluoro-2′-nitro-biphenyl claim 21 , 4′-chloro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′-dichloro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′-difluoro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′ claim 21 ,5′-trifluoro-biphenyl-2-ylamine claim 21 , 3′-chloro-4′ claim 21 ,5′-difluoro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′-dichloro-5-fluoro-biphenyl-2-ylamine or 3′ claim 21 ,5′-dichloro-4′-fluoro-biphenyl-2-ylamine.28. The process of claim 21 , wherein the palladium source is a palladium(II) salt or a palladium(0) complex.29. The process of claim 21 , wherein the palladium source claim 21 , calculated on the basis of the Pd content claim 21 , is used in an amount of from 0.0001 mol % to 0.5 mol % claim 21 , relative to 1 mol of compound II or compound IV claim 21 , if these are used in equimolar amounts claim 21 , or claim 21 , if compounds II and IV are not used in equimolar amounts claim 21 , relative to 1 mol of that compound II or IV which is not used in excess.30. The process of claim 29 , wherein the palladium ...

DIBENZOTHIOPHENE SALT AS ALKYNYLATING AND CYANATING AGENT

The present invention describes a new alkynylation and cyanation agent, as well as its preparation and use to introduce nitrile (cyano) or alkyne groups into chemical target molecules by means of an electrophilic reaction. To enable an electrophilic reaction, the chemical backbone of dibenzothiophene was used. 114-. (canceled)16. The salt according to claim 15 , wherein R is an R′silyl group claim 15 , wherein the three R′ substituents are independently selected from the group consisting of: optionally substituted linear claim 15 , branched or cyclic Chydrocarbon groups optionally having one or more unsaturated bonds and optionally one or more heteroatoms.17. The salt according to claim 15 , wherein R and the three R′ substituents of the R′silyl group are independently selected from the group consisting of: optionally substituted Ccycloalkenyl groups having one or more unsaturated C—C double bonds claim 15 , optionally substituted Caryl groups claim 15 , optionally substituted Ccycloalkyl groups claim 15 , optionally substituted Calkyl groups claim 15 , optionally substituted Calkenyl groups having one or more unsaturated C—C double bonds claim 15 , optionally substituted Calkynyl groups claim 15 , optionally substituted Cheteroalkyl groups claim 15 , optionally substituted Cheteroalkenyl groups having one or more unsaturated double bonds claim 15 , optionally substituted Cheteroalkynyl groups optionally having one or more unsaturated bonds claim 15 , optionally substituted Cheteroaryl groups claim 15 , optionally substituted Cheterocycloalkyl groups claim 15 , optionally substituted Cheterocycloalkenyl groups having one or more unsaturated double bonds.18. The salt according to claim 15 , wherein the compound of formula I or formula II represents the cation and the anion is selected from the group consisting of: triflate (TfO); perchlorates; nitrate; TfN; [{3 claim 15 ,5-(CF)CH}B]; PF6; BF4; B(CF); BF; BR* claim 15 , wherein R* is optionally substituted Calkyl ...

COMPOSITIONS AND METHODS OF PROMOTING ORGANIC PHOTOCATALYSIS

The invention provides novel compounds and methods that are useful in promoting reactions that proceed through an oxidative quenching pathway. In certain embodiments, the reactions comprise atom transfer radical polymerization. 1. A method of promoting reaction of at least one reagent , wherein the reaction comprises a quenching step , wherein the method comprises irradiating the at least one reagent in the presence of an organic compound with an excited-state reduction potential that is equal to or more negative than about −1.0 V vs. SCE.2. The method of claim 1 , wherein the excited state comprises a singlet or triplet excited state.3. The method of claim 1 , wherein the excited-state reduction potential is equal to or more negative than one selected from the group consisting of about −2.4 V vs. SCE claim 1 , −2.3 V vs. SCE claim 1 , about −2.2 V vs. SCE claim 1 , about −2.1 V vs. SCE claim 1 , about −2.0 V vs. SCE and about −1.5 V vs. SCE.4. The method of claim 1 , wherein the reaction comprises at least one selected from the group consisting of atom transfer radical addition/polymerization claim 1 , dehalogenation claim 1 , cycloaddition claim 1 , cyclization claim 1 , dimerization claim 1 , coupling claim 1 , reduction claim 1 , ring-opening claim 1 , alkylation claim 1 , arylation claim 1 , oxygenation claim 1 , energy transfer claim 1 , and radical addition.5. The method of claim 1 , wherein the reaction comprises atom transfer radical addition/polymerization.6. The method of claim 1 , wherein the at least one reagent comprises a (meth)acrylate and an organic halide.7. The method of claim 6 , wherein the organic halide comprises an α-halo ester.8. The method of claim 1 , wherein the reaction is essentially free of a metal or metalloid.9. The method of claim 1 , wherein the radiation comprises visible light.10. The method of claim 9 , wherein the radiation comprises sunlight or a natural light source.11. The method of claim 9 , wherein the radiation comprises ...

ETHYLENE-TO-LIQUIDS SYSTEMS AND METHODS

The present disclosure provides petrochemical processing methods and systems, including ethylene conversion processes and systems, for the production of higher hydrocarbon compositions, for example liquid hydrocarbon compounds, with reduced amount of unsaturated hydrocarbons. 1. (canceled)2. The method of claim 8 , wherein the at least one mesoporous catalyst comprises mesoporous zeolites.3. The method of claim 2 , wherein the mesoporous zeolites comprise mesoporous ZSM-5.4. The method of claim 8 , wherein the C compounds are generated at a selectivity greater than about 50%.57.-. (canceled)8. A method for generating hydrocarbon compounds with three or more carbon atoms (C compounds) claim 8 , comprising:{'sub': 2', '4', '2', '2', '2', '4', '2', '2', '4', '2', '2', '4', '3+, 'directing a feed stream comprising ethylene (CH), hydrogen (H), and carbon dioxide (CO) at a CH/Hmolar ratio from about 0.01 to 5, and a CH/COmolar ratio from about 1 to 10, into an ethylene conversion reactor that converts said CHin an ethylene conversion process to yield a product stream comprising said C compounds,'}wherein said ethylene conversion reactor comprises at least one mesoporous catalyst disposed therein and configured to facilitate said ethylene conversion process, and wherein said at least one mesoporous catalyst comprises a plurality of mesopores having an average pore size from about 1 nanometer (nm) to 500 nm.9. The method of claim 8 , wherein the C compounds comprise hydrocarbon compounds with five or more carbon atoms (C compounds).10. The method of claim 8 , wherein the ethylene conversion reactor is an ethylene-to-liquids (ETL) reactor claim 8 , and wherein the ethylene conversion process is an ETL process.11. The method of claim 8 , wherein the average pore size is from 1 nm to 50 nm.12. The method of claim 8 , wherein the average pore size is from 1 nm to 10 nm.13. The method of claim 8 , wherein the CH/Hmolar ratio is between about 0.1 and about 2.14. The method of ...

Complexes

The present invention provides a palladium(II) complex of formula (1) or a palladium(II) complex of formula (2). 137-. (canceled)39. The palladium(II) complex of claim 38 , wherein Rand Rare the same and are cyclohexyl.40. The palladium(II) complex of claim 38 , wherein Rand Rare claim 38 , independently claim 38 , —H claim 38 , substituted or unsubstituted straight-chain alkyl claim 38 , substituted or unsubstituted branched-chain alkyl claim 38 , substituted or unsubstituted cycloalkyl claim 38 , substituted or unsubstituted alkoxy claim 38 , substituted or unsubstituted aryl claim 38 , substituted or unsubstituted heteroaryl claim 38 , substituted or unsubstituted —N(alkyl)(wherein the alkyl groups are the same or different and are claim 38 , independently claim 38 , a straight-chain or branched-chain group) claim 38 , substituted or unsubstituted —N(cycloalkyl)(wherein the cycloalkyl groups are the same or different) claim 38 , substituted or unsubstituted —N(aryl)(wherein the aryl groups are the same or different) claim 38 , substituted or unsubstituted —N(heteroaryl)(wherein the heteroaryl groups are the same or different) or substituted or unsubstituted heterocycloalkyl.41. The palladium(II) complex of claim 40 , wherein both of Rand Rare —H.42. The palladium(II) complex of claim 38 , wherein Rand Rare claim 38 , independently claim 38 , —H claim 38 , substituted or unsubstituted straight-chain alkyl claim 38 , substituted or unsubstituted branched-chain alkyl claim 38 , substituted or unsubstituted cycloalkyl claim 38 , substituted or unsubstituted alkoxy claim 38 , substituted or unsubstituted -thioalkyl claim 38 , substituted or unsubstituted aryl claim 38 , substituted or unsubstituted heteroaryl claim 38 , substituted or unsubstituted —N(alkyl)(wherein the alkyl groups are the same or different and are claim 38 , independently claim 38 , straight-chain or branched-chain group) claim 38 , substituted or unsubstituted —N(cycloalkyl)(wherein the cycloalkyl ...

RUTHENIUM-CATALYZED SYNTHESIS OF BIARYL COMPOUNDS IN WATER

Using a [RuCl(arene)]complex and a formate source, a directed ortho C—H insertion and aryl-aryl coupling sequence in water provides biaryl compounds useful in the preparation of biologically active molecules and intermediates. Reactions may be conducted in the ambient atmosphere. Ruthenium catalysts prepared from [RuCl(arene)]and a formate source may be prepared in situ or isolated for later use. 1. A method of preparing a biaryl compound in water comprising:{'sub': 2', '2, 'reacting a first aryl compound with a second aryl compound in water in the presence of a catalytically effective amount of a [RuCl(arene)]complex and an effective amount of a source of formate;'}the first aryl compound comprising first and second ring atoms, the second ring atom having a directing group appended thereto and being located ortho to the first ring atom;the second aryl compound comprising a first ring atom, the first ring atom being substituted with a leaving group;wherein the reacting of the first aryl compound with the second aryl compound forms a bond between the first ring atom of the first aryl compound and the first ring atom of the second aryl compound.37-. (canceled)8. The method of claim 1 , wherein the formate source is an alkali metal formate claim 1 , alkaline earth metal formate claim 1 , N(R)HC(O)O claim 1 , HC(O)—OCalkyl claim 1 , sodium thioformate claim 1 , sodium formamide claim 1 , glyoxal claim 1 , sodium glyoxalate or potassium glyoxalates claim 1 , or a combination thereof; and Ris hydrogen or Calkyl.9. (canceled)10. The method of claim 1 , wherein the first aryl compound comprises a first 6-membered carbocyclic ring claim 1 , the first 6-membered carbocyclic ring comprising the first and second ring atoms of the first aryl compound.1112-. (canceled)13. The method of claim 1 , wherein the second aryl compound comprises a 5-6-membered heteroaryl ring claim 1 , the 5-6-membered heteroaryl ring comprising the first ring atom of the second aryl compound and the ...

Metathesis Catalyst

The current invention describes new metathesis catalysts, a method for their preparation and their use in metathesis reactions. 1. Compounds of formula (I)Ru stands for ruthenium,R1 stands for alkyl,R2 stands for alkyl,R3 stands for an electron-withdrawing substituent,Hal stands for chlorine or bromine, independently of each other,Lig stands for the ligand Lig1 or Lig2.in which The current invention describes new metathesis catalysts, a method for their preparation and their use.Numerous metathesis catalysts are already known; refer to for example: Tetrahedron Lett. 1999, 40, 1091-1094, J. Am. Chem. Soc. 2000, 122, 58-71, Angew. Chem. 2003, 115, 1944-1968. It is known from these publications that substrates comprising acetal-groups considerably inhibit metathesis reactions.New metathesis catalysts comprising acetal-groups with the formula (I) have been found in whichIt was further found that the catalysts of formula (I) can be produced from compounds of formula (II)In which R1, R2 and R3 have the above given meanings, by reaction with 2generation Grubbs catalyst (see Aldrich Chemistry Handbook Fine Chemicals 2009-2010, page 1453) in the presence of CuCl (J. Org. Chem. 2004, 69, 6894-6896).It was finally found out that the catalysts of formula (I) are suitable for the modification of butadiene acrylonitrile copolymers.whereinEspecially preferred are catalysts of formula (I), in whichwhereinPreparation of the catalyst of formula (I), wherein R1=Me, R2=C12H25, R3=NO2, Hal=C1, Lig=Lig1.In a Schlenk apparatus, the 2-generation Grubbs catalyst (0.108 g, 0.13 mmol) is mixed with a solution of compound (I-1):(0.059 g, 0.14 mmol) in 5 ml dichloromethane and 25 mg of copper-(I)-chloride and was stirred for about 50 minutes to about 60 minutes at ambient temperature under an argon atmosphere. The solvent was then removed under vacuum and the residue was purified by column chromatography. The catalyst (I) was obtained as a green solid.Preparation of the catalyst of formula (I), ...

Highly active multidentate catalysts for efficient alkyne metathesis

The invention relates to highly active and selective catalysts for alkyne metathesis. In one aspect, the invention includes a multidentate organic ligand wherein one substrate-binding site of the metal center is blocked. In another aspect, the invention includes N-quaternized or silane-based multidentate organic ligands, capable of binding to metals. In yet another aspect, the invention includes N-quaternized or silane-based multidentate catalysts. The catalysts of the invention show high robustness, strong resistance to small alkyne polymerization and significantly enhanced catalytic activity compared to their corresponding non-quaternized or non-silane-based multidentate catalyst analogues.

COMPLEX AND STRUCTURALLY DIVERSE COMPOUNDS

The invention provides a novel, general, and facile strategy for the creation of small molecules with high structural and stereochemical complexity. Aspects of the methods include ring system distortion reactions that are systematically applied to rapidly convert readily available natural products to structurally complex compounds with diverse molecular architectures. Through evaluation of chemical properties including fraction of spcarbons, ClogP, and the number of stereogenic centers, these compounds are shown to be significantly more complex and diverse than those in standard screening collections. This approach is demonstrated with natural products (gibberellic acid, adrenosterone, and quinine) from three different structural classes, and methods are described for the application of this strategy to any suitable natural product. 1. A method for preparing a high-throughput screening library comprising:a) carrying out a ring expansion reaction, a ring fusion reaction, a ring rearrangement reaction, a ring cleavage reaction, or a combination thereof, on a natural product or a derivative thereof, wherein the natural product has high structural and stereochemical complexity;b) carrying out an oxidation reaction, a reduction reaction, an esterification, an amidation, an addition reaction, a substitution reaction, an elimination reaction, an aromatization reaction, a functional group transformation, or a protection reaction; optionally followed by carrying out an additional ring expansion reaction, a ring fusion reaction, a ring rearrangement reaction, or a ring cleavage reaction; andc) repeating steps a) and b) multiple times using different selections of reactions to provide a series of products for a high-throughput screening library;wherein the products comprise at least one ring distortion compared to the natural product; the products comprise at least three oxygen atoms, or at least two oxygen atoms and three nitrogen atoms; the products comprise at least two ...

NI(0) CATALYSTS

Provided herein are nickel(O) catalysts that are stable when exposed to air and can be used to catalyze the formation of a C—C, C—O, or C—N bond. 2. The catalyst of claim 1 , wherein the dashed line represents a double bond.3. The catalyst of or claim 1 , wherein each Ris the same.4. The catalyst of any one of to claim 1 , wherein Ris selected from the group consisting of methyl claim 1 , ethyl claim 1 , propyl claim 1 , isopropyl claim 1 , butyl claim 1 , sec-butyl claim 1 , isobutyl claim 1 , t-butyl claim 1 , pentyl claim 1 , 3-pentyl claim 1 , and diphenylmethyl.5. The catalyst of any one of to claim 1 , wherein Ris H.6. The catalyst of any one of to claim 1 , wherein each Ris the same.7. The catalyst of any one of to claim 1 , wherein each Ris selected from H claim 1 , chloro claim 1 , and methyl.8. The catalyst of any one of to claim 1 , wherein both Rtogether with the carbons to which they are attached form a 6-membered ring.9. The catalyst of any one of to claim 1 , wherein Ris aryl.10. The catalyst of claim 9 , wherein Ris phenyl.11. The catalyst of any one of to claim 9 , wherein Ris Calkyl.12. The catalyst of claim 11 , wherein Ris methyl or ethyl.13. The catalyst of any one of to claim 11 , wherein Ris H.14. The catalyst of any one of to claim 11 , wherein Ris Calkylene-aryl.15. The catalyst of claim 14 , wherein Ris Calkylene-aryl.16. The catalyst of or claim 14 , wherein the aryl of Rcomprises phenyl or naphthyl.17. The catalyst of claim 16 , wherein Ris toluyl claim 16 , methoxyphenyl claim 16 , tri(alkyl)phenyl (e.g. claim 16 , trimethylphenyl or triisopropylphenyl) claim 16 , MeCO-phenyl claim 16 , or phenyl.18. The catalyst of any one of to claim 16 , wherein Ris Calkylene-Calkene.19. The catalyst of claim 18 , wherein Ris Calkylene-Calkene.20. The catalyst of claim 18 , wherein Ris Calkylene-Calkene.21. The catalyst of any one of to claim 18 , wherein the Calkene is Calkene.22. The catalyst of any one of to claim 18 , wherein Ris Calkyl.23. The ...

SURFACE-MODIFIED CALCIUM CARBONATE AS CARRIER FOR TRANSITION METAL-BASED CATALYSTS

The present invention relates to a catalyst system comprising a transition metal compound on a solid carrier which is a surface-reacted calcium carbonate. The invention further relates to a method for manufacturing said catalyst system and to its use in heterogeneous catalysis. 1. A catalyst system comprising a transition metal compound on a solid carrier , wherein the solid carrier is a surface-reacted calcium carbonate comprising ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC) , and at least one water-insoluble calcium salt other than calcium carbonate , and wherein the surface-reacted calcium carbonate shows:{'sup': '2', '(i) a specific surface area of from 15 to 200 m/g measured using nitrogen and the BET method according to ISO 9277:2010;'}(ii) an intra-particle intruded specific pore volume in the range of from 0.1 to2. 3 cm/g calculated from mercury porosimetry measurement; and(iii) a ratio of the at least one water-insoluble calcium salt to calcite, aragonite and/or vaterite in the range of from 1:99 to 99:1 by weight.2. The catalyst system according to claim 1 , wherein the at least one water-insoluble calcium salt is selected from the group consisting of octacalcium phosphate claim 1 , hydroxylapatite claim 1 , chlorapatite claim 1 , fluorapatite claim 1 , carbonate apatite and mixtures thereof claim 1 , preferably the at least one water-insoluble calcium salt is hydroxylapatite.3. The catalyst system according to claim 1 , wherein the ratio of the at least one water-insoluble calcium salt to calcite claim 1 , aragonite and/or vaterite claim 1 , preferably to calcite claim 1 , is in the range of from 1:9 to 9:1 claim 1 , preferably from 1:7 to 8:1 claim 1 , more preferably from 1:5 to 7:1 and even more preferably from 1:4 to 7:1 by weight4. The catalyst system according to claim 1 , wherein the transition metal compound is selected from the group consisting of palladium compounds claim 1 , platinum compounds claim 1 , copper ...

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

A process of converting a carbon-carbon multiple bond to a cyclopropane ring, comprising the addition of a N-alkyl-N-nitroso compound to a mixture of alkene precursor, aqueous base and Pd(II)-catalyst, with the N-alkyl-N-nitroso compound obtained directly from an alkyl amine derivative, NaNOand an acid via phase separation of the N-alkyl-N-nitroso compound from the aqueous phase. 1. A process of ring formation across a carbon-carbon multiple bond , the process comprising the steps of reacting a N-alkyl-N-nitroso compound with a substrate bearing a carbon-carbon multiple bond , wherein the N-alkyl-N-nitroso compound is generated in-situ , and the N-alkyl-N-nitroso compound is added to the substrate without being first isolated.2. The process according to wherein the N-alkyl-N-nitroso compound is an organic solution of N-alkyl-N-nitroso urea claim 1 , and wherein the N-alkyl-N-nitroso urea is added to the substrate without being first isolated in solid form.3. The process according to wherein the N-alkyl-N-nitroso compound is a N-methyl-N-nitroso compound (MNC).4. The process according to wherein the N-alkyl-N-nitroso compound is selected from the group consisting of N-methyl-N-nitroso-urea (MNU) claim 1 , N-methyl-N-nitroso-p-toluenesulfonamide claim 1 , N-nitroso-dimethylurethane claim 1 , nitroso-EMU and N-nitroso-β-methylaminoisobutyl methyl ketone (NMK).5. The process according to wherein the N-alkyl-N-nitroso compound is generated in-situ from a mixture of a HNRR′ compound claim 1 , water claim 1 , NaNOand an acid claim 1 , before partitioning into an organic solvent to form an organic solution of N-alkyl-N-nitroso compound.6. The process according to wherein the N-alkyl-N-nitroso compound is formed in-situ from a N-alkylamine.7. The process according to claim 1 , wherein a biphasic mixture is formed with the N-alkyl-N-nitroso compound in an organic layer.8. The process according to claim 1 , wherein the N-alkyl-N-nitroso compound in liquid phase is separated ...

POLYMER-SUPPORTED TRANSITION CATALYST

A long life catalyst is provided that is conveniently and inexpensively capable of being produced and that is highly active and has inhibited metal leakage. According to aspects of the present invention, a catalyst is provided that includes: a polymer including a plurality of first structural units and a plurality of second structural units; and metal acting as a catalytic center, wherein at least part of the metal is covered with the polymer, each of the plurality of first structural units has a first atom constituting a main chain of the polymer and a first substituent group bonded to the first atom, a second atom included in each of the plurality of second structural units is bonded to the first atom, and the second atom is different from the first atom, or at least one of all substituent groups on the second atom is different from the first substituent group. 2. The catalyst of claim 1 ,wherein the main chain of the polymer does not include a carbon atom.3. The catalyst of claim 1 ,wherein each of the first atom and the second atom is not a carbon atom.4. The catalyst of claim 1 ,wherein the first atom is a silicon atom.5. The catalyst of claim 1 ,wherein the second atom is an oxygen atom or a nitrogen atom.6. The catalyst of claim 1 ,wherein the metal is any one of selected from the group consisting of palladium, platinum, ruthenium, rhodium, silver, gold, copper, nickel, cobalt, iron, chromium, manganese, technetium, osmium, molybdenum, tungsten, iridium, rhenium, titanium, zirconium, hafnium, tantalum, niobium, and vanadium.7. The catalyst of claim 1 , the first atom is a silicon atom; and', 'the first substituent group is at least any one selected from the group consisting of a substituent group constituted only of a hydrogen atom, a substituent group including an oxygen atom, and a substituent group including a carbon atom., 'wherein8. The catalyst of claim 1 , further comprising an inorganic member or an organic member.9. The catalyst of claim 1 , further ...

Process for the Preparation of Idnanones

A process of forming compounds of formula I 2. (canceled)3. The process according to claim 1 , wherein the amino compound HNR is an alkylamide claim 1 , and R represents —(CO)Me or —(CO)Et.4. The process according to claim 1 , wherein the amino compound HNR is a sulfonamide claim 1 , and R represents —SOMe claim 1 , —SOEt or —SOPhMe.5. The process according to claim 1 , wherein the amino compound HNR is a carbamate claim 1 , and R represents —COMe claim 1 , —COEt. The present invention relates to the field of organic synthesis. It provides a novel process of preparing indanones, which are compounds of formula I:In particular, it provides a process of preparing compounds of formula I from α-substituted cinnamic aldehydes.Some indanones have been described in literature as useful fragrance ingredients. For example, WO03072533 A1 describes the use of 3,3-dimethyl indanones in perfumery with leathery, woody and saffron-like odours. U.S. Pat. No. 3,944,679 disclosed 2- and 3-alkyl substituted indanones have coumarin-like odors when imparted to tobacco, foods and drinks flavors.Often the synthetic pathway of indanones is somewhat complicated and the preparation has to be performed in several individual steps, adding to the costs of said compounds.The synthesis of indenol esters and indenol ethers from cinnamic aldehydes has been disclosed in U.S. Pat. No. 7,250,528 B2. Said compounds can be further converted to the corresponding indanones (Womack, G. B. et al; J. Org. Chem. 2009, 74, 5738-5741; Womack, G. B. et al; J. Org. Chem. 2007, 72, 7046-7049).Alternatively, indanones can be obtained from cinnamic aldehydes in a stepwise conversion via indenyl sulfonamides (Fan, X. et al; Chem. Comm. 2014, 50, 4119-4122) or indenyl carbamates (Kraft, W. M.; J. Am. Chem. Soc. 1948, 70, 3569-3571).There remains a need to provide a simple and cost efficient process of producing compounds of formula I.The invention provides in a first aspect a process of making a compound of formula (I) ...

BISMUTH PERFLUOROALKYLPHOSPHINATES AS LEWIS ACID CATALYSTS

The invention relates to bismuth perfluoroalkylphosphinates as Lewis acid catalysts, the compounds, and processes for the preparation thereof. 1. Compounds the formula (Ia) or (Ib){'br': None, 'sub': x', 'f', '2', '3-x, 'ArBi[OP(O)(R)]\u2003\u2003(Ia),'}{'br': None, 'sub': 3', 'f', '2', '2, 'ArBi[OP(O)(R)]\u2003\u2003(Ib)'}whereAr in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms, which may be unsubstituted or substituted;{'sub': 'f', 'Rin each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms and'}x denotes 0, 1 or 2.2. Compounds according to claim 1 , where Ar is identical on each occurrence.3. Compounds according to claim 1 , where the perfluoroalkyl group Ris identical on each occurrence.4. Compounds according to claim 1 , where Ris selected from pentafluoroethyl or n-nonafluorobutyl.5. Process for the preparation of compounds of the formula (Ia) according to claim 1 , where x denotes 0 claim 1 , characterised in that bismuth is reacted with a compound of the formula (II){'br': None, 'sub': f', '2, 'HOP(O)(R)\u2003\u2003(II),'}where{'sub': 'f', 'Rin each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms.'}6. Process for the preparation of compounds of the formula (Ia) according to claim 1 , where x denotes 1 or 2 claim 1 , characterised in that a compound of the formula (II){'br': None, 'sub': f', '2, 'HOP(O)(R)\u2003\u2003(II),'}where{'sub': 'f', 'Rin each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms,'}is reacted with triarylbismuthane, where the aryl in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms.7. Process for the preparation of compounds of the formula (Ib) according to claim 1 , characterised in that triarylbismuthane is converted to triaryldichlorobismuthane claim 1 , where ...

METAL PARTICLE-CHITIN COMPOSITE MATERIALS AND METHODS OF MAKING THEREOF

Methods for making metal particle-chitin composite materials are described. The methods can comprise contacting an ionic liquid with chitin, thereby forming a mixture; contacting the mixture with a non-solvent, thereby forming a chitin substrate in the non-solvent; collecting the chitin substrate from the non-solvent; deacetylating the collected chitin substrate, thereby forming a deacetylated chitin substrate; contacting the deacetylated chitin substrate with a metal salt, thereby forming an impregnated precursor composite material; and contacting the impregnated precursor composite material with a reducing agent, thereby reducing the metal salt to form a plurality of metal particles dispersed on the chitin substrate and forming the metal particle-chitin composite material. 1. A method of making a metal particle-chitin composite material comprising:contacting an ionic liquid with chitin, thereby forming a mixture;contacting the mixture with a non-solvent, thereby forming a chitin substrate in the non-solvent;collecting the chitin substrate from the non-solvent;deacetylating the collected chitin substrate, thereby forming a deacetylated chitin substrate;contacting the deacetylated chitin substrate with a metal salt, thereby forming an impregnated precursor composite material; andcontacting the impregnated precursor composite material with a reducing agent, thereby reducing the metal salt to form a plurality of metal particles dispersed on the chitin substrate and forming the metal particle-chitin composite material.3. The method of claim 1 , wherein the ionic liquid contains an imidazolium cation.4. The method of claim 1 , wherein the ionic liquid is a 1-alkyl-3-alkyl imidazolium C-Ccarboxylate.5. The method of claim 1 , wherein the concentration of chitin in the mixture is from 0.1 wt % to 25 wt %.6. The method of claim 1 , wherein the non-solvent is water claim 1 , a C-Calcohol claim 1 , ketone claim 1 , or a mixture thereof.7. The method of claim 1 , further ...

CATALYSTS FOR EFFICIENT Z-SELECTIVE METATHESIS

The present application provides, among other things, compounds and methods for metathesis reactions. In some embodiments, provided compounds promote highly efficient and highly Z-selective metathesis. In some embodiments, provided compounds and methods are particularly useful for producing allyl alcohols. In some embodiments, provided compounds have the structure of formula I. In some embodiments, provided compounds comprise ruthenium, and a ligand bonded to ruthenium through a sulfur atom. 3. The compound of claim 1 , wherein Rand L are covalently linked claim 1 , and each of Rand Ris bonded to M through sulfur.7. The compound of claim 6 , wherein Z is —O— claim 6 , —S— claim 6 , —Se— claim 6 , —N(R)— claim 6 , —N═ claim 6 , —P(R)— claim 6 , —C(O)— claim 6 , —C(S)— claim 6 , —S(O)— claim 6 , or —Se(O)— claim 6 , and Ris R.8. The compound of claim 6 , wherein —Z—Ris halogen.11. The compound of claim 10 , wherein each of X and Y is —S—.12. The compound of claim 11 , wherein r is 1.13. The compound of claim 12 , wherein Ris NHC.14. The compound of claim 13 , wherein Z is —O—.16. The compound of claim 1 , wherein the compound is dimerized or polymerized.17. The compound of claim 1 , wherein the compound is linked to a tag or a solid support.19. A method for preparing a compound of claim 1 , comprising steps of:a) providing a first compound of formula I; and{'sup': '14', 'b) replacing the Rand L groups of the first compound to provide a second compound of formula I, wherein the first compound and the second compound are different.'}20. A method for performing a metathesis reaction claim 1 , comprising providing a compound of . The present application claims priority to U.S. Provisional Application Ser. No. 61/834,050, filed Jun. 12, 2013, the entirety of which is incorporated herein by reference.This invention was made with government support under Grant No. CHE-1111074 awarded by the National Science Foundation. The US government has certain rights in the invention. ...

METHODS AND COMPOSITIONS FOR TERPENOID SYNTHESIS

In one aspect, the disclosure relates to methods for preparation of terpene and terpene-like molecules. In a further aspect, the disclosure relates to the products of the disclosed methods, i.e., terpene and terpene-like molecules prepared using the disclosed methods. Intermediates for the synthesis of a wide variety of terpenoids are γ-allyl Knoevenagel adducts or quasi γ-allyl Knoevenagel adducts are disclosed. In various aspects, methods of preparing terpenoids through these intermediates are disclosed. The methods can comprise a-alkylation of an allylic electrophile followed by ring-closure metathesis to a polycyclic terpenoid structure. In a further aspect, the disclosure pertains to terpenoid frameworks, and compounds prepared via disclosed oxidation and substitution reactions on the disclosed terpenoid frameworks. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure. 13. The method of claim 8 , wherein X is acetoxy claim 8 , t-butyloxycarbonoxy claim 8 , or Br.15. The method of claim 1 , further comprising:reacting the γ-allyl Knoevenagel adduct or a quasi γ-allyl Knoevenagel adduct with an allyl comprising electrophile to form an α,γ-diallyl Knoevenagel adduct or quasi α,γ-diallyl Knoevenagel adduct; andcatalyzing a ring-closure metathesis of the α,γ-diallyl Knoevenagel adduct or quasi α,γ-diallyl Knoevenagel adduct thereby forming a compound with a terpenoid framework. This Application claims the benefit of U.S. Provisional Application No. 62/394,852, filed on Sep. 15, 2016, which is incorporated herein by reference in its entirety.Structurally complex terpenoid natural products have been recognized as important therapeutic agents. Many terpenoid natural products contain a polycyclic core bearing a medium-sized 7- to 9-membered ring; examples of which are illustrated in . For example, taxol and ingenol are clinically used for the treatment of cancer and ...

Organic compounds

A process of converting a carbon-carbon multiple bond to a cyclopropane ring, comprising the addition of a N-alkyl-N-nitroso compound to a mixture of alkene precursor, aqueous base and Pd(II)-catalyst, with the N-alkyl-N-nitroso compound obtained directly from an alkyl amine derivative, NaNO 2 and an acid via phase separation of the N-alkyl-N-nitroso compound from the aqueous phase.

POLYMER-SUPPORTED TRANSITION CATALYST

A long life catalyst is provided that is conveniently and inexpensively capable of being produced and that is highly active and has inhibited metal leakage. According to aspects of the present invention, a catalyst is provided that includes: a polymer including a plurality of first structural units and a plurality of second structural units; and metal acting as a catalytic center, wherein at least part of the metal is covered with the polymer, each of the plurality of first structural units has a first atom constituting a main chain of the polymer and a first substituent group bonded to the first atom, a second atom included in each of the plurality of second structural units is bonded to the first atom, and the second atom is different from the first atom, or at least one of all substituent groups on the second atom is different from the first substituent group. 1. A catalyst , comprising:a polymer including a plurality of first structural units and a plurality of second structural units; and at least part of the metal is covered with the polymer;', 'each of the plurality of first structural units has a first atom constituting a main chain of the polymer and a first substituent group bonded to the first atom,', 'a second atom included in each of the plurality of second structural units is bonded to the first atom; and', 'the second atom is different from the first atom, or at least one of all substituent groups on the second atom is different from the first substituent group., 'a metal acting as a catalytic center, wherein2. The catalyst of claim 1 , wherein the main chain of the polymer does not include a carbon atom.3. The catalyst of claim 1 , wherein each of the first atom and the second atom is not a carbon atom.4. The catalyst of claim 1 , wherein the first atom is a silicon atom.5. The catalyst of claim 1 , wherein the second atom is an oxygen atom or a nitrogen atom.6. The catalyst of claim 1 , wherein the metal is any one of selected from the group ...

TRI-(ADAMANTYL)PHOSPHINES AND APPLICATIONS THEREOF

In one aspect, phosphine compounds comprising three adamantyl moieties (PAd) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAdligands are also provided for catalytic synthesis including catalytic cross-coupling reactions. 1. A method of synthesizing a tri-(adamantyl)phosphine compound , PAd , comprising:{'sub': 2', '2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphine (PAd) and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}2. The method of claim 1 , wherein adamantyl moieties (Ad) of the PAdare independently selected from the group consisting of adamantane claim 1 , diamantane claim 1 , triamantane and derivatives thereof.3. The method of claim 1 , wherein the substituted adamantyl moiety comprises a leaving group.4. The method of claim 3 , wherein the leaving group is selected from the group consisting of acetate claim 3 , triflate claim 3 , tosylate and hydroxyl.5. The method of claim 1 , wherein yield of the PAdis greater than 50 percent.6. The method of claim 1 , wherein yield of the PAdis greater than 60 percent.7. A method of cross-coupling comprising:{'sub': '3', 'providing a reaction mixture including a substrate, a coupling partner and a transition metal complex comprising PAdligand; and'}reacting the substrate and coupling partner in the presence of the transition metal complex or derivative thereof to provide cross-coupled reaction product.8. The method of claim 7 , wherein the transition metal complex comprises one or more metals selected from Group VIIIA claim 7 , IB or IIB of the Periodic Table.9. The method of claim 7 , wherein the transition metal complex comprises ...

Reaction medium containing water-surfactant mixture

The present invention is directed to reaction mixtures comprising a water-surfactant mixture and a co-solvent. This technology reduced the amount of organic solvents needed for performing chemical reactions. Furthermore, compared to reaction mixtures lacking the co-solvent, solvation of the reactants and products of the chemical reaction is greatly enhanced, leading to a significantly improved yield, purity, reproducibility and robustness.

Compositions Comprising TPGS-750-M

In one embodiment, the present application discloses mixtures comprising (a) water in an amount of at least 1% wt/wt of the mixture; (b) a transition metal catalyst; and (c) one or more solubilizing agents; and methods for using such mixtures for performing transition metal mediated bond formation reactions. 114.-. (canceled)16. The compound of wherein n is an integer selected from 10 to 50.17. The compound of wherein n is an integer selected from 16 to 20.18. The compound of claim 15 , wherein n is 15.20. The mixture of claim 19 , where n is 15.21. The mixture of claim 19 , wherein the transition metal catalyst is selected from an organo-palladium or -nickel reagent claim 19 , organo-copper or -gold reagent claim 19 , organo-rhodium or -iridium complex claim 19 , or an organo-ruthenium claim 19 , -iron claim 19 , or -osmium reagent claim 19 , wherein the catalyst is capable of promoting cross-coupling reactions claim 19 , or other reactions characteristic of catalysis by these metals claim 19 , that form a carbon-carbon claim 19 , carbon-heteroatom or carbon-hydrogen bond.22. The mixture of claim 19 , wherein the transition metal catalyst comprises less than 5 mole % claim 19 , less than 3 mole % or less than 2 mole % of the mixture.23. The mixture of claim 19 , further comprising (i) a coupling substrate and (ii) a coupling partner.24. The mixture of claim 23 , wherein water is the sole solvent.25. The mixture of claim 24 , wherein the coupling substrate is selected from substituted or unsubstituted alkyl claim 24 , substituted or unsubstituted heteroalkyl claim 24 , substituted or unsubstituted cycloalkyl claim 24 , substituted or unsubstituted heterocycloalkyl claim 24 , substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl; and wherein the coupling partner is selected from H claim 24 , substituted or unsubstituted amine claim 24 , substituted or unsubstituted silane claim 24 , substituted or unsubstituted alkyl claim 24 , substituted or ...

Surfactant-Enabled Transition Metal-Catalyzed Chemistry

In one embodiment, the present application discloses mixtures comprising (a) water in an amount of at least 1% wt/wt of the mixture; (b) a transition metal catalyst; and (c) one or more solubilizing agents; and methods for using such mixtures for performing transition metal mediated bond formation reactions. 114.-. (canceled)16. The mixture of claim 15 , wherein the non-aqueous solvent or solvent mixtures is selected from the group consisting of methanol claim 15 , ethanol claim 15 , propanol claim 15 , isopropanol claim 15 , n-butanol claim 15 , acetone claim 15 , ethyl acetate claim 15 , methyl acetate claim 15 , THF claim 15 , acetonitrile claim 15 , ethyleneglycol or PEGs claim 15 , dioxane claim 15 , MIBK claim 15 , MEK claim 15 , DMA or mixtures thereof.17. The mixture of claim 16 , wherein the non-aqueous solvent or solvent mixtures is selected from the group consisting of propanol claim 16 , isopropanol claim 16 , acetone claim 16 , THF claim 16 , ethyleneglycol or PEGs or mixtures thereof.18. The mixture of claim 15 , wherein the transition metal catalyst is selected from an organo-palladium or -nickel reagent claim 15 , organo-copper or -gold reagent claim 15 , organo-rhodium or -iridium complex claim 15 , or an organo-ruthenium claim 15 , -iron claim 15 , or -osmium reagent claim 15 , wherein the catalyst is capable of promoting cross-coupling reactions claim 15 , or other reactions characteristic of catalysis by these metals claim 15 , that form a carbon-carbon claim 15 , carbon-heteroatom or carbon-hydrogen bond.19. The mixture of claim 15 , wherein the transition metal catalyst comprises less than 5 mole % claim 15 , less than 3 mole % or less than 2 mole % of the mixture.20. The mixture of claim 15 , further comprising (i) a coupling substrate and (ii) a coupling partner.21. The mixture of claim 16 , wherein the coupling substrate is selected from substituted or unsubstituted alkyl claim 16 , substituted or unsubstituted heteroalkyl claim 16 , ...

NANO-TO-NANO FE/PPM Pd CATALYSIS OF CROSS-COUPLING REACTIONS IN WATER

In one embodiment, the present application discloses a catalyst composition comprising: a) a reaction solvent or a reaction medium; b) organometallic nanoparticles comprising: i) a nanoparticle (NP) catalyst, prepared by a reduction of an iron salt in an organic solvent, wherein the catalyst comprises at least one other metal selected from the group consisting of Pd, Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or mixtures thereof; c) a ligand; and d) a surfactant; wherein the metal or mixtures thereof is present in less than or equal to 50,000 ppm relative to the iron salt. 120.-. (canceled)21. An aqueous micellar composition in a reaction solvent for enabling cross-coupling reactions containing organometallic nanoparticles (NPs) as catalyst , comprising:a) an element selected from the group consisting of Fe, C, H, O, Mg, and a halide, or the entire combination thereof; andb) palladium (Pd), or at least one other metal selected from the group consisting of Pt, Au, Ni, Co, Cu and Mn, or a mixture thereof; wherein the catalyst (NPs) is prepared from a reduction of an iron salt or an iron complex in a solvent and in the presence of a ligand using a reducing agent.22. The aqueous micellar composition of claim 22 , wherein the iron is selected from the group consisting of a Fe(II) or Fe(III) salt claim 22 , a Fe(II) salt precursor or Fe(III) salt precursor.23. The aqueous micellar composition of claim 21 , wherein the Pd is naturally present in the iron salt or the iron complex in amounts less than or equal to 1 ppm claim 21 , 10 ppm claim 21 , 50 ppm claim 21 , 100 ppm claim 21 , 200 ppm claim 21 , 300 ppm claim 21 , 400 ppm or 500 ppm relative to the iron salt or iron complex.24. The aqueous micellar composition of claim 23 , where the amount of Pd present is controlled by external addition of a palladium salt to an iron salt.25. The aqueous micellar composition of claim 23 , wherein the reducing reagent is a Grignard reagent selected from the group consisting of MeMgCl ...

Build Sequences for Mechanosynthesis

Processes for creating build sequences are described which use computational chemistry algorithms to simulate mechanosynthetic reactions, and which may use the mechanosynthesis process conditions or equipment limitations in these simulations, and which facilitate determining a set of mechanosynthetic reactions that will build an atomically-precise workpiece with a desired degree of reliability. Included are methods for error correction of pathological reactions or avoidance of pathological reactions. Libraries of reactions may be used to reduce simulation requirements. 1. A method of creating a build sequence for a workpiece , comprising:a. storing the atomic coordinates of the workpiece in a data storage means;b. using computation chemistry algorithms in conjunction with computing means, coupled to the data storage means, to determine a set of mechanosynthetic reactions sufficient to build the workpiece; andc. determining an order in which said mechanosynthetic reactions may be performed to result in the workpiece.2. The method of further comprising:a. assessing the reliability of one or more of the mechanosynthetic reactions; andb. revising the build sequence if the reliability is insufficient.3. The method of wherein the order in which said mechanosynthetic reactions are performed is determined at least in part by steric considerations.4. The method of wherein the order in which mechanosynthetic reactions are performed is determined at least in part to avoid undesired rearrangements in intermediate workpiece structures.5. The method of wherein determining a set of mechanosynthetic reactions is done by choosing from a set of known mechanosynthetic reactions.6. The method of wherein one or more of the mechanosynthetic reactions use a plurality of tips simultaneously.7. The method of wherein the computational chemistry algorithms simulate the use of atomically-precise tips.8. The method of wherein the atomically-precise tips are comprised of adamantane-like ...

Cannabinoid Compositions Having Improved Bioactivity and Methods Thereof

A composition for the activation (decarboxylation) and improved bioavailability of acid-form cannabinoids is provided. The composition includes dried Cannabis sativa L, such as dried hemp flower, dried food powder, and at least one catalyst, selected from dried citrus juice, lemon juice or composition thereof. The dried Cannabis sativa L is combined with the dried food powder including at least one catalyst for cold decarboxylation and improved bioavailability of cannabinoids. Preferably the catalyst becomes immediately effective when the composition is mixed into an aqueous solution for consumption. The composition is also endowed with a cytochrome p450 enzyme inhibitor in the form of dried food powder having an ascorbic acid content, or other enzyme inhibitor, in sufficient amount to inhibit hepatic enzymes in vivo and improve the bio-effects of the cannabinoids.

CARBON MONOXIDE-RELEASING MOLECULES FOR THERAPEUTIC APPLICATIONS AND METHODS FOR THE PREPARATION AND USE THEREOF

Carbon monoxide-releasing organic molecules are described herein. The molecules can be synthesized prior to administration (e.g., ex vivo) or formed in vivo. In those embodiments where the molecules are formed in vivo, reactants are administered under physiological conditions and undergo a cycloaddition reaction to form a product which releases carbon monoxide. In applying such reactions for therapeutic applications in vivo, the cycloaddition and CO release typically occur only under near-physiological or physiological conditions. For example, in some embodiments, the cycloaddition reaction and/or release of carbon monoxide occur at a temperature of about 37° C. and pH of about 7.4. Pharmaceutical compositions and methods for release carbon monoxide are also described. 2. The compound of claim 1 , wherein Rand Rare hydrogen.3. The compound of claim 2 , wherein subscript n is 1 or 2.4. The compound of claim 1 , wherein X is NRand Ris selected from the group consisting of hydrogen claim 1 , alkyl claim 1 , and heteroalkyl.5. The compound of claim 4 , wherein Rand Rare hydrogen.6. The compound of claim 5 , wherein subscript n is 1 or 2.7. A method for generating carbon monoxide in vivo or ex vivo claim 5 , the method comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'allowing a precursor molecule according to to react to form an organic molecule that releases carbon monoxide under physiological conditions.'}8. The method of claim 7 , wherein the carbon monoxide is released in an amount effective for the treatment of inflammation claim 7 , cardiovascular disease claim 7 , cancer claim 7 , sepsis claim 7 , or a combination thereof.9. The method of claim 8 , wherein Rand Rare hydrogen.10. The method of claim 9 , wherein subscript n is 1 or 2.11. The method of claim 8 , wherein X is NRand Ris selected from the group consisting of hydrogen claim 8 , alkyl claim 8 , and heteroalkyl.12. The method of claim 11 , wherein Rand Rare hydrogen.13. The method of claim 12 ...

Process for producing aromatic compound, and palladium complex

A process for producing an aromatic compound in high yield and a palladium complex are provided. The palladium complex is represented by formula (D) or formula (D′): In formula (D), X represents a chlorine atom, A represents an alkyl group having 1 to 3 carbon atoms, B represents an alkyl group having 4 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, or an alkoxy group having 1 to 20 carbon atoms, and R 6 , R 7 and R 8 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms. In formula (D′), X, A, B and R 4 to R 8 are the same as defined above.

Processo para preparação de olefinas aromáticas

METHODS USED IN MICRO-CHANNEL REACTORS WITH A TIED CATALYST AND A BOUND CATALYST OR BOUND CHIRAL TOOLS

α-二亚胺镍金属有机配体、多孔有机聚合物及其应用

本公开提供了α‑二亚胺镍金属有机配体、多孔有机聚合物及其应用，多孔有机聚合物包括如下化学结构式： 本公开提供的多孔有机聚合物能够获得用于催化Suzuki偶联反应的催化剂，且该催化剂的催化活性高、成本低，使用量少，而且能够重复利用。

Catalyst system comprising transition metal and imidazoline-2-ylidene or imidazolidine-2-ylidene

This invention provides a catalyst system useful in many coupling reactions, such as Suzuki, Kumada, Heck, and amination reactions. The catalyst system of the present invention makes use of N-heterocyclic carbenes or their protonated salts. The composition of the catalyst system comprises at least one transition metal compound and at least one N-heterocyclic carbene or its protonated salt. This invention further provides novel N-heterocyclic carbenes and their protonated salts. One type of N-heterocyclic carbene used in this invention is an imidazolinc-2-ylidene wherein the 1 and 3 positions are each, independently, substituted by an aromatic group in which each ortho position is, independently, substituted by a secondary or tertiary group which has at least three atoms.

Use a catalyst system comprising nickel palladium or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in stille coupling reactions

This invention provides a process for conducting Stille coupling reactions. The processes of the present invention make use of N-heterocyclic carbenes as ancillary ligands in Stille couplings of aryl halides. A Stille coupling can be carried out by mixing, in a liquid medium, at least one strong base; at least one aryl halide or aryl pseudohalide in which all substituents are other than stannyl groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom; at least one organotin compound wherein the tin atom is quaternary, wherein one group bound to the tin atom is unsaturated at the alpha or beta position, and wherein each of the remaining groups bound to the tin atom is a saturated group; at least one metal compound comprising at least one metal atom selected from nickel, palladium, and platinum, wherein the formal oxidation state of the metal is zero or two; and at least one N-heterocyclic carbene. One preferred type of N-heterocyclic carbene is an imidazoline-2-ylidene of the formula wherein R 1 and R 2 are each, independently, alkyl or aryl groups having at least 3 carbon atoms, R 3 and R 4 are each, independently, a hydrogen atom, a halogen atom, or a hydrocarbyl group.

Use of a catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in kumada coupling reactions

This invention provides a process for conducting Kumada coupling reactions. The processes of the present invention make use of N-heterocyclic carbenes as ancillary ligands in Kumada couplings of aryl halides. A Kumada coupling can be carried out by mixing, in a liquid medium, at least one aryl halide, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom; at least one Grignard reagent; at least one metal compound comprising at least one metal atom selected from nickel, palladium, and platinum, wherein the formal oxidation state of the metal is zero or two; and at least one N-heterocyclic carbene. One preferred type of N-heterocyclic carbene is an imidazoline-2-ylidene of the formula wherein R 1 and R 2 are each, independently, alkyl or aryl groups having at least 3 carbon atoms, R 3 and R 4 are each, independently, a hydrogen atom, a halogen atom, or a hydrocarbyl group. Homocoupling of aryl pseudohalides is also feasible using the processes of this invention.

Use of catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in amination reactions

This invention provides a process for conducting amination reactions. The processes of the present invention make use of N-heterocyclic carbenes as ancillary ligands in aminations of aryl halides and aryl pseudohalides. An amination can be carried out by mixing, in a liquid medium, at least one strong base; at least one aryl halide or aryl pseudohalide in which all substituents are other than amino groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom; at least one primary amine and/or at least one secondary amine; at least one metal compound comprising at least one metal atom selected from nickel, palladium, and platinum, wherein the formal oxidation state of the metal is zero or two; and at least one N-heterocyclic carbene. One preferred type of N-heterocyclic carbene is an imidazoline-2-ylidene of the formula wherein R 1 and R 2 are each, independently, alkyl or aryl groups having at least 3 carbon atoms, R 3 and R 4 are each, independently, a hydrogen atom, a halogen atom, or a hydrocarbyl group.

Use of a catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene of imidazolidine-2-ylidene in suzuki coupling reactions

This invention provides a process for conducting Suzuki coupling reactions. The processes of the present invention make use of N-heterocyclic carbenes as ancillary ligands in Suzuki couplings of aryl halides and aryl pseudohalides. A Suzuki coupling can be carried out by mixing, in a liquid medium, at least one strong base; at least one aryl halide or aryl pseudohalide in which all substituents are other than boronic acid groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom; at least one arylboronic acid in which all substituents are other than chlorine atoms, bromine atoms, iodine atoms, or pseudohalide groups; at least one metal compound comprising at least one metal atom selected from nickel, palladium, and platinum, wherein the formal oxidation state of the metal is zero or two; and at least one N-heterocyclic carbene. One preferred type of N-heterocyclic carbene is an imidazoline-2-ylidene of the formula wherein R 1 and R 2 are each, independently, alkyl or aryl groups having at least 3 carbon atoms, R 3 and R 4 are each, independently, a hydrogen atom, a halogen atom, or a hydrocarbyl group.

Catalyzed coupling reactions of aryl halides with silanes

A process for conducting coupling reactions of aryl halides with unsaturated silanes is described. The processes use N-heterocyclic carbenes as ancillary ligands in these coupling reactions. A coupling of an aryl halide with an unsaturated silane can be carried out by mixing, in a liquid medium, at least one strong base; at least one aryl halide or aryl pseudohalide in which all substituents are other than silyl groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one chlorine atom, bromine atom, or iodine atom; at least one silane wherein the silicon atom is quaternary, wherein one group bound to the silicon atom is unsaturated at the alpha or beta position, and wherein each of the remaining groups bound to the silicon atom is a saturated hydrocarbyl or a saturated hydrocarbyloxy group; at least one nickel, palladium, or platinum compound, wherein the formal oxidation state of the metal is zero or two; and at least one N-heterocyclic carbene. One preferred type of N-heterocyclic carbene is an imidazoline-2-ylidene of the formula wherein R 1 and R 2 are each, independently, alkyl or aryl groups having at least 3 carbon atoms, R 3 and R 4 are each, independently, a hydrogen atom, a halogen atom, or a hydrocarbyl group.

Transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals

The invention relates to novel transition metal complexes containing at least one diaminocarbene ligand, to processes for preparing these transition metal complexes and to their use as catalysts in organic reactions.