Transfer Hydrogenation of Cyclopamine Analogs

Provided herein is a process for the transfer-hydrogenation of ketone analogs of members of the jervine type of Veratrum alkaloids, such as cyclopamine. Also provided herein are novel ruthenium transfer-hydrogenation catalysts.

TRANSFER HYDROGENATION OF CYCLOPAMINE ANALOGS

Provided herein is a process for the transfer-hydrogenation of ketone analogs of members of the jervine type of alkaloids, such as cyclopamine. Also provided herein are novel ruthenium transfer-hydrogenation catalysts. 3. The process of wherein the ring carbon atom that is directly attached to the hydroxyl group on the compound of formula (II-AA) has an (S) stereochemical configuration and Ris hydrogen in the β-position.4. The process of claim 1 , wherein the ruthenium transfer-hydrogenation catalyst comprises an amino alcohol ligand.5. The process of claim 4 , wherein the amino alcohol ligand is achiral.7. The process of claim 6 , wherein Rand Rare both —CHand Ris —CHCH.8. The process of claim 1 , wherein the ruthenium transfer-hydrogenation catalyst comprises an optionally substituted benzene ligand.9. The process according to claim 8 , wherein the optionally substituted benzene ligand is selected from benzene claim 8 , mesitylene claim 8 , p-cymene claim 8 , and hexamethylbenzene.10. The process according to claim 9 , wherein the ruthenium transfer-hydrogenation catalyst is generated from (hexamethylbenzene)ruthenium chloride dimer and an achiral amino alcohol.14. The process according to claim 13 , wherein Xis chloro.17. The process of claim 16 , wherein Rand Rare each methyl claim 16 , Ris ethyl claim 16 , each of R claim 16 , R claim 16 , R claim 16 , R claim 16 , R claim 16 , and Ris methyl claim 16 , and Xis Cl.18. The process of claim 1 , wherein the hydrogen donor is an organic alcohol.19. The process of claim 18 , wherein the reducing is carried out in an ether solvent.20. The process of claim 19 , wherein the reducing is carried out at a temperature of about 10° C. to about 40° C.21. The process of claim 19 , wherein the reducing is carried out in the presence of base. This application is a continuation of U.S. patent application Ser. No. 13/232,851, filed Sep. 14, 2011, now allowed, which claims the benefit of U.S. Provisional Patent Application No. 61/ ...

ENANTIOPURE TERPHENYLS WITH TWO ORTHO-ATROPISOMERIC AXES

Enantiopure terphenyl presenting two ortho-located chiral axes having the following structural formula (I): their process of synthesis and their use as mono or bidentate ligands for asymmetric organometallic reactions, as organocatalysts, as chiral base and as generator, with metal, of isolable chiral metallic complexes for applications in asymmetric catalysis and others. 2. The enantiopure terphenyl according to claim 1 , wherein{'sub': '1', 'claim-text': an halogen atom,', 'a substituted or unsubstituted branched or straight alkyl group or', 'a substituted or unsubstituted branched or straight alkoxy group or', {'sub': '3', 'a CFgroup,'}], 'Rrepresents'}{'sub': '2', 'claim-text': a hydrogen atom or', 'a substituted or unsubstituted branched or straight alkyl group, or', 'a substituted or unsubstituted branched or straight alkoxy group, 'Rrepresents'}{'sub': '3', 'claim-text': a substituted or unsubstituted branched or straight alkyl group or', 'a substituted or unsubstituted branched or straight alkoxy group,, 'Rrepresents'}{'sub': '4', 'claim-text': a hydrogen atom or', 'a halogen atom or', 'a substituted or unsubstituted branched or straight alkoxy group, or', 'a substituted or unsubstituted branched or straight alkyl group or', 'a aryl group or', {'sub': 2', '2', 'n+2, 'a CHF group, or a CHFgroup or —CnFgroup avec n=1 à 10, or'}], 'Rrepresents'}{'sub': '5', 'claim-text': [{'sub': a', 'a', '1', '4, 'a SORgroup with Rselected from a substituted or unsubstituted branched or straight-(C-C) alkyl group or a substituted or unsubstituted aryl group, or'}, 'a OH group, or', {'sub': a', 'd', 'a', 'd', 'a', 'd, '—PRnor a —P(O)Rnwith Rand Rindependently selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group,'}], 'Rrepresents'}{'sub': '6', 'claim-text': a hydrogen atom,', 'a halogen atom or', {'sub': 1', '4, 'a substituted or unsubstituted branched or straight-(C-C) alkyl group or'}, {'sub': 1', '4, 'a ...

PHOSPHINE LIGANDS FOR CATALYTIC REACTIONS

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions. 130-. (canceled)33. The method of claim 31 , wherein X is attached to an atom of Aradjacent to the atom bonded to Ar.35. The method of claim 34 , wherein Rand Rare hydrogen.36. The method of claim 34 , wherein Rand Rtogether with the carbon atom to which they are attached form a 3- claim 34 , 4- claim 34 , 5- claim 34 , 6- claim 34 , or 7-membered spirocyclic ring containing 0 claim 34 , 1 claim 34 , or 2 ring heteroatoms.38. The method of claim 31 , wherein Arand Arare each aryl.39. The method of claim 31 , wherein Aris substituted with two Rand Aris substituted with three R.40. The method of claim 31 , wherein Ris alkyloxy and wherein Ris alkyl.41. The method of claim 31 , wherein Ris isopropyl.43. The method of claim 42 , wherein Rtogether with Rform a 5-membered spiro ring containing two heteroatoms.44. The method of claim 43 , wherein the two heteroatoms are each oxygen.45. The method of claim 31 , wherein R claim 31 , R claim 31 , R claim 31 , and Rare each methyl.48. The method of claim 47 , wherein the compound is selected from the group consisting of:2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinane;2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-one;2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-ol;7,7,9,9-tetramethyl-8-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,4-dioxa-8-phosphaspiro[4.5]decane;8,8,10,10-tetramethyl-9-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,5-dioxa-9-phosphaspiro[5.5]undecane;3,3,8,8,10,10-hexamethyl-9-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,5-dioxa-9-phosphaspiro[5.5]undecane;1-(2′-(dimethylamino)-6′-methoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-bis(dimethylamino)biphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-dimethoxybiphenyl-2 ...

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions.

Controlled Radical Polymerization, and Catalysts Useful Therein

A catalyst is prepared in situ by reaction between an aryl halide and a Ni-ligand complex. The catalyst may be used to promote chain-growth polymerization of halogen-substituted Mg or Zn monomers. Polymers, copolymers, block copolymers, polymer thin films, and surface-confined polymer brushes may be produced using the catalyst.

METHOD FOR PRODUCING RUTHENIUM COMPLEX

The present invention relates to a method for efficiently producing a ruthenium complex (1) by reacting a dinuclear ruthenium complex (2) with a compound (3) in the presence of a primary alcohol and a base. The ruthenium complex (1) can also be efficiently produced by treating a dinuclear ruthenium complex (4) with a primary alcohol and a base. (In the formulas, solid lines, triple lines, broken lines, C, H, N, OP, Ru, X, AH and Rto Rhave the meanings defined in the specification.) 3. The production method according to claim 1 , wherein AH is a benzene which may have an alkyl group.4. The production method according to claim 1 , wherein X is a chloride ion.5. The production method according to claim 1 , wherein all of R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , Rand Rare a hydrogen atom.6. The production method according to claim 1 , wherein each of R claim 1 , R claim 1 , Rand Ris independently a group selected from the group consisting of an alkyl group claim 1 , a cycloalkyl group claim 1 , and an aryl group which may have a substituent.9. The production method according to claim 7 , wherein X is a chloride ion.10. The production method according to claim 7 , wherein all of R claim 7 , R claim 7 , R claim 7 , R claim 7 , R claim 7 , R claim 7 , Rand Rare a hydrogen atom.11. The production method according to claim 7 , wherein each of R claim 7 , R claim 7 , Rand Ris independently a group selected from the group consisting of an alkyl group claim 7 , a cycloalkyl group claim 7 , and an aryl group which may have a substituent. The present invention relates to a method for producing [bis(2-phosphinoethyl)amine]carbonylhalohydridoruthenium(II) which is a kind of ruthenium complex exhibiting excellent catalytic activity in a hydrogenation reaction.It has been reported that {bis[2-(diphenylphosphino)-ethyl]amine}carbonylchlorohydridoruthenium(II) [Ru-MACHO (registered trademark), hereinafter the same] which is a kind of ruthenium complex ...

PHOSPHINE LIGANDS FOR CATALYTIC REACTIONS

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions. 130-. (canceled)32. The process of claim 31 , wherein the ligand is selected from a group consisting of:2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinane;2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-one;2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-ol;7,7,9,9-tetramethyl-8-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,4-dioxa-8-phosphaspiro[4.5]decane;8,8,10,10-tetramethyl-9-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,5-dioxa-9-phosphaspiro[5.5]undecane;3,3,8,8,10,10-hexamethyl-9-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,5-dioxa-9-phosphaspiro[5.5]undecane;1-(2′-(dimethylamino)-6′-methoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-bis(dimethylamino)biphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-dimethoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-diisopropoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′-(dimethylamino)biphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(biphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(1,1′-binaphthyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′-methoxy-1,1′-binaphthyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;2,2,6,6-tetramethyl-1-(2-(naphthalen-1-yl)phenyl)phosphinan-4-one;2,2,6,6-tetramethyl-1-(2-(naphthalen-2-yl)phenyl)phosphinan-4-one;2,2,6,6-Tetramethyl-1-(1′,3′,5′-triphenyl-1′H-1,4′-bipyrazol-5-yl)phosphinan-4-one;2,2,6,6-tetramethyl-1-(1-phenyl-1H-pyrazol-5-yl)phosphinan-4-one;1-(2-(1H-pyrrol-1-yl)phenyl)-2,2,6,6-tetramethylphosphinan-4-one;1-(3,6-dimethoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(3,6-dimethoxy-2′,4′,6′-trimethylbiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropyl-3,6-dimethoxybiphenyl-2-yl)phosphinan-4-one;2,2,6,6- ...

Manganese based complexes and uses thereof for homogeneous catalysis

The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C—C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a hydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

Controlled radical polymerization, and catalysts useful therein

A catalyst is prepared in situ by reaction between an aryl halide and a Ni(0) complex. The catalyst may be used to promote chain-growth polymerization of halogen- substituted Mg or Zn monomers by a controlled radical mechanism. Polymers, copolymers, block copolymers, polymer thin films, and surface-confined polymer brushes may be produced using the catalyst.

Controlled radical polymerization, and catalysts useful therein

A catalyst is prepared in situ by reaction between an aryl halide and a Ni(0) complex. The catalyst may be used to promote chain-growth polymerization of halogen- substituted Mg or Zn monomers by a controlled radical mechanism. Polymers, copolymers, block copolymers, polymer thin films, and surface-confined polymer brushes may be produced using the catalyst.

Controlled radical polymerization, and catalysts useful therein

A catalyst is prepared in situ by reaction between an aryl halide and a Ni(0) complex. The catalyst may be used to promote chain-growth polymerization of halogen-substituted Mg or Zn monomers by a controlled radical mechanism. Polymers, co-polymers, block copolymers, polymer thin films, and surface-confined polymer brushes may be produced using the catalyst.

Procesos para preparar compuestos antivirales

Se divulgan: (a) procesos para preparar un compuesto y sales del mismo que, entre otras aplicaciones, son útiles para inhibir el virus de hepatitis C (HCV); (b) intermediarios útiles en la preparación del compuesto y sales; (c) composiciones farmacéuticas que comprenden el compuesto o sales; y (d) métodos para usar dichas composiciones.

用于制备抗病毒化合物的方法

本公开涉及：(a)用于制备特别是用于抑制丙型肝炎病毒(HCV)的化合物及其盐的方法；(b)用于制备所述化合物和盐的中间体；(c)包含所述化合物或盐的药物组合物；以及(d)使用这类组合物的方法。

Trivalent phosphorus cyclic compounds, preparation methods thereof and homogeneously soluble catalyst systems comprising the same

본 발명은 신규 사이클릭 인(III) 화합물 및 이의 제조 방법에 대해 기술하고 있다. 인 화합물은 두 자리 리간드로서 작용하여 금속, 특히 주기율표의 8족 금속과 함께 착화합물을 형성하며, 이 착화합물은 촉매 시스템의 성분으로서 사용될 수 있다. The present invention describes novel cyclic phosphorus (III) compounds and methods for their preparation. Phosphorus compounds act as bidentate ligands to form complexes with metals, especially Group 8 metals of the periodic table, which can be used as components of the catalyst system.

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) methods of using such phosphacycle ligands in bond forming reactions; and (c) methods of preparing phosphacycle ligands.

Process for preparing antiviral compounds

This disclosure is directed to: (a) processes for preparing a compound and salts thereof that, inter alia, are useful for inhibiting hepatitis C virus (HCV); (b) intermediates useful for the preparation of the compound and salts; (c) pharmaceutical compositions comprising the compound or salts; and (d) methods of use of such compositions.

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions.

Process for preparing antiviral compounds

This disclosure is directed to: (a) processes for preparing compounds and salts thereof that, inter alia, are useful for inhibiting hepatitis C virus (HCV); (b) intermediates useful for the preparation of the compounds and salts; (c) pharmaceutical compositions comprising the compounds or salts; and (d) methods of use of such compositions.

Process for preparing antiviral compounds

This disclosure is directed to: (a) processes for preparing compounds and salts thereof that, inter alia, are useful for inhibiting hepatitis C virus (HCV); (b) intermediates useful for the preparation of the compounds and salts; (c) pharmaceutical compositions comprising the compounds or salts; and (d) methods of use of such compositions.

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions.

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions.

Process for preparing antiviral compounds

This disclosure is directed to: (a) processes for preparing compounds and salts thereof that, inter alia, are useful for inhibiting hepatitis C virus (HCV); (b) intermediates useful for the preparation of the compounds and salts; (c) pharmaceutical compositions comprising the compounds or salts; and (d) methods of use of such compositions.

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions.

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) methods of using such phosphacycle ligands in bond forming reactions; and (c) methods of preparing phosphacycle ligands.

Phosphorane and diphosphorane, metal complexes thereof, use thereof and method of asymmetric hydrogenation

Asymmetric catalysis based on chiral phospholanes and hydroxyl phospholanes

Chiral phosphine ligands derived from chiral natural products including D-mannitol and tartaric acid. The ligands contain one or more 5-membered phospholane rings with multiple chiral centers, and provide high stereoselectivity in asymmetric reactions.

Catalyst system for synthesizing phenylacetic acid from toluene

本发明公开了一种甲苯合成苯乙酸的催化剂体系，反应路线如下所示：

Asymmetric bidentate coordinating cmpds - for prepn of hydrogenation catalysts giving optically active products

Title cpds are of formula (I) or (II): R1R2X-XR1R2 (I) (where X=P, As or Sb, R1=hydrocarbon having >=1 asymmetric C and opt. heteroatoms, R2=aliphatic, cycloaliphatic or aromatic hydrocarbon residue, opt. substd, and R3=divalent hydrocarbon having >=1 asymmetric C atom and opt. heteroatoms). These cpds form complexes with transition metals, esp. Rh, which are useful as hydrogenation catalysts for olefins or acetylenes to give opt. active prods. The cpds may be prepd by reaction of a cpd of formula R2X(M)-X(M)R2 (where M=alkali metal) with an optically active alkyl or aryl tosylate or chloride.

Patent FR2190830B1

Diphosphine ligands

Compounds of the formulae I and Ia in the form of mixtures of diastereomers or pure diastereomers, (I), (Ia), where R1 is a hydrogen atom or C1-C4-alkyl and R'1 is C1-C4-alkyl; X1 and X2 are each, independently of one another, a sec-phosphino group; T is C6-C20-arylene or C4-C18- heteroarylene having heteroatoms selected from the group consisting of O, S, -N= and N(C1-C4-alkyl); v is 0 or an integer from 1 to 4; X1 is bound in the ortho position relative to the T-C* bond; Q is vinyl, methyl, ethyl, -CH2-OR, -CH2-N(C1-C4-alkyl)2 or a C- or S-bonded chiral group which directs metals of metallation reagents into the ortho position; R is hydrogen, a silyl radical or an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic hydrocarbon radical which has from 1 to 18 carbon atoms and is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, F or CF3; are ligands for metal complexes as homogeneous catalyst in asymmetric syntheses.

Process for preparing a complex

FUNCTIONALIZED FERROCENYLDIPHOSPINE, METHOD FOR THEIR PRODUCTION AND THEIR USE

Diphosphine ligands

Transfer hydrogenation of cyclopamine analogs

Provided herein is a process for the transfer-hydrogenation of ketone analogs of members of the jervine type of Veratrum alkaloids, such as cyclopamine. Also provided herein are novel ruthenium transfer-hydrogenation catalysts.

Method for producing ruthenium complex

The present invention pertains to a method for efficiently producing a ruthenium complex (1A) by reacting a binuclear ruthenium complex (2A) with a compound (3A) in the presence of a primary alcohol and a base. The ruthenium complex (1A) can also be efficiently produced by allowing a primary alcohol and a base to act on a binuclear ruthenium complex (4A). (In the formulas, solid lines, triple lines, dashed lines, C, H, N, OP, Ru, X, AH and R1 to R12 have the meanings defined in the specification.)

Bisphosphine, process for producing the same, and use thereof

Process for preparing n-(6-(3-tert-butyl-5-(2,4-dioxo-3,4-dihydropyrimidin-1-(2h)-yl)-2-methoxyphenyl)naphthalen-2-yl)methanesulfonamide

This disclosure is directed to: (a) processes for preparing a compound and salts thereof that, inter alia, are useful for inhibiting hepatitis C virus (HCV); (b) intermediates useful for the preparation of the compound and salts; (c) pharmaceutical compositions comprising the compound or salts; and (d) methods of use of such compositions.

Process for preparing antiviral compounds

본 발명의 교시내용은, (a) 특히, C형 간염 바이러스(HCV)를 억제하는데 유용한 화합물 및 이의 염의 제조 방법; (b) 상기 화합물과 염을 제조하는데 유용한 중간체들; (c) 상기 화합물 또는 염을 포함하는 약제학적 조성물들; (d) 상기 조성물들의 사용 방법에 관한 것이다. The teachings of the present invention include (a) methods of making compounds and salts thereof useful for inhibiting hepatitis C virus (HCV) in particular; (b) intermediates useful in preparing the compounds and salts; (c) pharmaceutical compositions comprising said compound or salt; (d) methods of using the compositions.

Tertiary phosphines containing alkylene glycol groups

A compound is disclosed having the formula (I), in which m equals 1 to 1000; x equals 0 to 4; W is a group of formulas -CH2-CH2-, -CH(CH3)CH2- or -CH2CH(CH3)-; R is hydrogen, a straight-chain or branched-chain C1-C5 alkyl radical; or a group of formulas (a) or (b), in which a, b, c, d and e independently represent a number from 0 to 1000, at least one of the numbers represented by a, b, c, d and e being higher than 0; R5, R6, R7, R8 and R9 are the same or different and represent hydrogen, C1-C5 alkyl or a group of formula (c); R1 and R2 are the same or different and represent a straight-chain, a branched-chain or a cyclic C1-C30 alkyl radical or C6-C10 aryl radical which is non-substituted or substituted by one to five C1-C3 alkyl radicals, or R1 and R2 form together with the trivalent P atom a dibenzophospholyl of formula (d) or a 3,4-dimethylphospholyl of formula (e); and L stands for C1-C5 alkyl, C1-C5 alkoxy, NO2, NR3R4, R3 and R4 independently representing hydrogen or C1-C4 alkyl, or for Cl or OH.

Catalyst system for selective oligomerization of ethylene, reaction method and application thereof

本发明提供了一种乙烯选择性齐聚的催化剂体系、反应方法及其应用，属于均相催化技术领域。该催化剂体系包括：配体a；过渡金属化合物b，过渡金属化合物b为IVB～VIII族的金属化合物；其中，配体a的结构通式如式(I)所示： R 1 和R 2 可以相同或不同，分别独立选自烷基、芳基或芳基的衍生物，但R 1 和R 2 至少有一个为芳基或芳基的衍生物；R 4 、R 5 与N、P、N不成环，或R 4 、R 5 与N、P、N形成多元环；R 3 ～R 10 可以相同或不同，分别独立选自氢、烷基或芳基。本发明的催化剂体系主要用于乙烯选择性齐聚，具有催化活性高、产物线性α‑烯烃选择性高、1‑丁烯含量少、C 6 ～C 8 线性α‑烯烃选择性高、聚合物副产物少的特点。

Process for preparing antiviral compounds

Tertiary phosphanes containing alkylene glycol groups

A compound is disclosed having the formula (I), in which m equals 1 to 1000; x equals 0 to 4; W is a group of formulas --CH 2 --CH 2 --, --CH(CH 3 )CH 2 -- or --CH 2 CH(CH 3 )--; R is hydrogen, a straight-chain or branched-chain C 1 -C 5 alkyl radical; or a group of formulas (a) or (b), in which a, b, c, d and e independently represent a number from 0 to 1000, at least one of the numbers represented by a, b, c, d and e being higher than 0; R 5 , R 6 , R 7 , R 8 and R 9 are the same or different and represent hydrogen, C 1 -C 5 alkyl or a group of formula (c); R 1 and R 2 are the same or different and represent a straight-chain, a branched-chain or a cyclic C 1 -C 30 alkyl radical or C 6 -C 10 aryl radical which is non-substituted or substituted by one to five C 1 -C 3 alkyl radicals, or R 1 and R 2 form together with the trivalent P atom form a dibenzophospholyl of formula (d) or a 3,4-dimethylphospholyl of formula (e); and L stands for C 1 -C 5 alkyl, C 1 -C 5 alkoxy, NO 2 , NR 3 R 4 , R 3 and R 4 independently representing hydrogen or C 1 -C 4 alkyl, or for Cl or OH. ##STR1##

Process for the carbonylation of a conjugated diene

Process for the carbonylation of a conjugated diene by reacting the conjugated diene with carbon monoxide and an hydroxyl group containing compound in the presence of a catalyst system based on: (a) a source of palladium cations, (b) a diphosphine ligand, and (c) a source of anions, wherein the diphosphine ligand is a ligand having the general formula I wherein x 1 and x 2 represent a cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and R represents a bivalent aliphatic bridging group, connecting both phosphorus atoms, containing from 2 to 4 atoms in the bridge, which is substituted with at least one substituent or R represents a phenyl group with both phosphorus groups bound to the 1,2-position.

Production of optically active phospholanes

The invention relates to phospholanes and diphospholanes of general formula (I), whereby R represents H, C1-C6-alkyl, aryl, alkyl aryl, SiR2 3, R2 represents alkyl or aryl, A represents H, C1-C6-alkyl, aryl, Cl, or (a), and B represents a binding link with 1-5 C-atoms between both P-atoms. The invention also relates to the use of said phospholanes and diphospholanes as a catalyst in asymmetric synthesis.

Process for hydroformylation and catalysts suitable for said process containing phosphorus compounds as ligands

(57)【要約】 錯体を形成することができるλ 3 ，σ 2 −リン化合物を配位子として含有している触媒を使用する、２００℃までの温度と７００バールまでの圧力での、配位子としてリン化合物含有している、元素の周期律表の第VIII亜族の遷移金属の錯体の存在下でのＣＯ／Ｈ 2 を用いたオレフィンのヒドロホルミル化によるアルデヒドの製造方法ならびに新規のホスファベンゼン。

Hydroformylation process and catalysts suitable therefor containing phosphorus compounds as ligands

本发明涉及在含磷化合物作为配体的元素周期表第VIII族过渡金属配合物存在下，在最高200℃的温度和最高700bar的压力下，用CO/H 2 使烯烃加氢甲酰化制备醛的方法中，所用催化剂有能形成配合物的λ 3 ，σ 2 -磷化合物作为配体。本发明还提供了新的磷杂苯。

Bisphosphine, process for producing the same, and use thereof

Bisphosphines represented by the general formula (I) wherein Ar 1 and Ar 2 each represents an arylene group which may be substituted; R 1 and R 2 each represents an alkyl group which may be substituted, or an aryl group which may be substituted, or R 1 and R 2 may combinedly form a ring together with the phosphorus atom bonded thereto; R 3 and R 4 each represents hydrogen atom or an alkyl group; and the carbon atoms each having R 3 and R 4 are bonded in positions ortho to the oxygen atom bonded to Ar 1 and Ar 2 : process for production thereof; Group VIII metal complexes comprising said bisphosphines; and process for producing aldehydes, which comprises, on hydroformylation of ethylenically unsaturated compounds with carbon monoxide and hydrogen, using said Group VIII metal complexes. The hydroformylation of ethylenically unsaturated compounds according to the present invention can produce n-aldehydes at higher reaction rate and industrially more advantageously than with catalysts comprising conventional phosphines, while suppressing side reactions such as hydrogenation and isomerization.

Patent TW283149B

Catalyst and process for the production of aldehydes by hydroformylation of olefinically unsaturated compounds

Katalysator, enthaltend Rhodium und eine Verbindung der allgemeinen Formel (I), worin m eine Zahl von 1 bis 1000; x eine Zahl von 0 bis 4; W eine Gruppe der Formeln -CH2-CH2-, -CH(CH3)CH2- oder -CH2CH(CH3)-; R Wasserstoff, ein geradkettiger oder verzweigter C1-C5-Alkylrest; oder eine Gruppe der Formeln (a) oder (b), wobei a, b, c, d und e unabhängig voneinander eine Zahl von 0 bis 1000, wobei mindestens eine der Zahlen a, b, c, d und e größer als 0 ist; R?5, R6, R7, R8 und R9¿ gleich oder verschieden sind und Wasserstoff, C¿1?-C5-Alkyl oder eine Gruppe der Formel (c) ist, R?1 und R2¿ gleich oder verschieden sind und einen geradkettigen, verzweigten oder cyclischen C¿1?-C30-Alkylrest oder C6-C10-Arylrest, der unsubstituiert oder durch ein bis fünf C1-C3-Alkylreste substituiert ist, und L C1-C5-Alkyl, C1-C5-Alkoxy, NO2, NR?3R4¿, wobei R?3 und R4¿ unabhängig voneinander Wasserstoff oder C¿1?-C4-Alkyl bedeuten, Cl oder OH bedeuten, für Hydroformylierungsreaktionen.

Procedure for preparing aldehydes and-or alcohols. (Machine-translation by Google Translate, not legally binding)

Process for preparing aldehydes and/or alcohols, in which olefins are reacted with carbon monoxide and hydrogen, in the presence of a complex catalyst comprising cobalt, carbon monoxide and a tertiary phosphine, characterized in that a catalyst containing a 5-member tertiary heterocyclic phosphine. (Machine-translation by Google Translate, not legally binding)

MANUFACTURE OF OPTICALLY ACTIVE PHOSPHOLANES

Bisphosphine, process for producing the same, and use thereof

A bisphosphine represented by the general formula (I): (I) (wherein Ar1 and Ar2 each represents arylene; R1 and R2 each represents alkyl or aryl or R1 and R2 may form a ring in cooperation with the phosphorus atom bonded thereto; R3 and R4 each represents hydrogen or alkyl; and the two carbon atoms each having R3 and R4 are bonded in positions ortho to the oxygen atom bonded to Ar1 and Ar2); a process for producing the bisphosphine; a Group VIII metal complex having the bisphosphine as a component; and a process in which an ethylenically unsaturated compound is hydroformylated with carbon monoxide and hydrogen with the aid of the Group VIII metal complex to produce the corresponding aldehyde. The hydroformylation of an ethylenically unsaturated compound can industrially advantageously produce an n-aldehyde at a high reaction rate while inhibiting side reactions such as hydrogenation and isomerization as compared with hydroformylation with existing bisphosphines.

Method for producing ruthenium complex

The present invention pertains to a method for efficiently producing a ruthenium complex (1A) by reacting a binuclear ruthenium complex (2A) with a compound (3A) in the presence of a primary alcohol and a base. The ruthenium complex (1A) can also be efficiently produced by allowing a primary alcohol and a base to act on a binuclear ruthenium complex (4A). (In the formulas, solid lines, triple lines, dashed lines, C, H, N, OP, Ru, X, AH and R1 to R12 have the meanings defined in the specification.)

Synthesis of phosphorus based ligands

Chiral ligands of the formula I or II, may be obtained in high enantiomeric purity from compounds of the formulae III or IV, respectively, with suitable phosphines, where the symbols R 1 , R, n, R 3 , R 4 , R' are as described in claim 1. The products may be converted into transition metal complexes which are useful as catalysts for asymmetric hydrogenation reactions.

Method for splitting chiral cyclophane alkyl sulfimide compound with external despinoid surface

本发明提供一种拆分外消旋面手性环芳烷磺酰亚胺类化合物的方法，所述方法以式I所示的环芳烷磺酰亚胺类化合物为底物，进行催化还原反应，得到面手性环芳烷磺酰亚胺类化合物(对映体过量可达92.1％)和面手性环芳烷磺酰胺类化合物(对映体过量可达93.0％，非对映体比例可达>20:1)，拆分系数可达到s＝80.2；催化还原反应的催化剂是镍的手性双膦配合物，由镍盐与手性双膦配体原位络合而成；本发明可以实现催化拆分，操作简单易行，催化剂商业可得，条件温和，能耗低，环境友好且拆分系数高，产率好。

Methods of preparing secondary carbinamine compounds with boronic acids

The present application relates to novel methods for the preparation of secondary carbinamine compounds, particularly the preparation of secondary carbinamine compounds of the formula Ia, formula Ib or formula IV from aldehydes of the formula II and boronic acids of the formula III or formula V, in the presence of ammonia or an ammonia equivalent of the formula NH4+X-.

Production of optically active phospholanes

The invention relates to phospholanes and diphospholanes of general formula (I), whereby R represents H, C1-C6-alkyl, aryl, alkyl aryl, SiR2 3, R2 represents alkyl or aryl, A represents H, C1-C6-alkyl, aryl, Cl, or (a), and B represents a binding link with 1-5 C-atoms between both P-atoms. The invention also relates to the use of said phospholanes and diphospholanes as a catalyst in asymmetric synthesis.

Production of optically active phospholanes

Enantiopure terphenyls with two ortho-atropisomeric axes

Phosphine compounds, transition metal complexes with the compounds contained as ligands therein, and asymmetric synthesis catalysts containing the complexes

Phosphine compounds represented by the following formula (1): wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 represent substituents, and asymmetric synthesis catalysts containing transition metal phosphine complexes with the compounds contained as ligands therein. The novel phosphine compounds according to the present invention are useful especially as ligands in transition metal complexes. The transition metal phosphine complexes are useful as catalysts for asymmetric synthetic reactions. The novel phosphine compounds useful as ligands can be prepared by a relatively economical preparation process. Further, use of these catalysts can afford hydrogenated products with high optically purity and is also extremely useful from the industrial standpoint.

Process for preparing antiviral compounds

Preparing a composition of primary alcohol, useful as softeners for plastics, comprises dimerization of a monoolefin in presence of aluminum catalyst, hydroformylation of the dimer followed by catalytic hydrogenation of obtained aldehyde

Preparation of a composition of 9-21C primary alcohol comprises: dimerization of 4-10C monoolefin containing internal and/or terminal double bonds in the presence of an aluminum catalyst (I); hydroformylation of the obtained olefin dimer composition by means of a carbon dioxide/hydrogen mixture in presence of a hydroformylation catalyst, which is homogeneously dissolved in a reaction medium; and catalytic hydrogenation of the obtained aldehyde composition to the corresponding alcohol. Preparation of a composition of 9-21C primary alcohol comprises: catalytic dimerization of 4-10C monoolefin containing internal and/or terminal double bonds; hydroformylation of the obtained olefin dimer composition by means of a carbon dioxide/hydrogen mixture in presence of hydroformylation catalyst, which is homogeneously dissolved in a reaction medium; and catalytic hydrogenation of the obtained aldehyde composition to the corresponding alcohol; where the dimerization is carried out at 160-260[deg]C in the presence of an aluminum catalyst (I) of formula AlRx(ORy)3x, and the hydroformylation is carried out in the presence of a rhodium complex dissolved in the reaction medium with a ligand containing phosphacyclohexane group, free ligand and optionally in the presence of a solvent at 50-250[deg]C and 10-100 bar. R, Ry : 1-10C alkyl; and x : 0-3.

Phosphine compounds, transition metal complexes with the compounds contained as ligands therein, and asymmetric synthesis catalysts containing the complexes

Phosphine compounds represented by the following formula (1): wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 represent substituents, and asymmetric synthesis catalysts containing transition metal phosphine complexes with the compounds contained as ligands therein. The novel phosphine compounds according to the present invention are useful especially as ligands in transition metal complexes. The transition metal phosphine complexes are useful as catalysts for asymmetric synthetic reactions. The novel phosphine compounds useful as ligands can be prepared by a relatively economical preparation process. Further, use of these catalysts can afford hydrogenated products with high optically purity and is also extremely useful from the industrial standpoint.

Phosphine compounds, transition metal complexes with the compounds contained as ligands therein, and asymmetric synthesis catalysts containing the complexes

Phosphine compounds represented by the following formula (1): wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 represent substituents, and asymmetric synthesis catalysts containing transition metal phosphine complexes with the compounds contained as ligands therein. The novel phosphine compounds according to the present invention are useful especially as ligands in transition metal complexes. The transition metal phosphine complexes are useful as catalysts for asymmetric synthetic reactions. The novel phosphine compounds useful as ligands can be prepared by a relatively economical preparation process. Further, use of these catalysts can afford hydrogenated products with high optically purity and is also extremely useful from the industrial standpoint.

Process for preparing antiviral compounds

This disclosure is directed to: (a) processes for preparing an intermediate useful for the preparation of a compound and salts thereof that, inter alia, are useful for inhibiting hepatitis C virus (HCV); (b) an intermediate useful for the preparation of the compound and salts; and (c) pharmaceutical compositions comprising the intermediate or salts.

Asymmetric catalysis based on chiral phospholanes and hydroxyl phospholanes

Chiral phosphine ligands derived from chiral natural products including D-mannitol and tartaric acid. The ligands contain one or more 5-membered phospholane rings with multiple chiral centers, and provide high stereoselectivity in asymmetric reactions.

[3.2.1] bridged ring lactone and lactam compounds and derivatives and preparation method thereof

一类[3.2.1]桥环内酯及内酰胺类化合物及其衍生物及制备方法，该化合物的结构通式如I所示：

Patent JPWO2021235518A1

Phosphine ligands for catalytic reactions

The disclosure is directed to: (a) phosphacycle ligands; (b) methods of using such phosphacycle ligands in bond forming reactions; and (c) methods of preparing phosphacycle ligands.

Cyclische verbindungen des dreiwertigen phosphors

一种含有双取代吲哚酮骨架的芳胺化合物及其合成方法

本发明公开了一种含有双取代吲哚酮骨架的芳胺化合物的合成方法，包括以下步骤：以3‑吡咯基羟吲哚和乙烯基苯并恶嗪酮为反应物，在手性草酰胺膦配体、三(二亚苄基丙酮)二钯‑氯仿加合物存在下，在有机溶剂中，反应得到含有双取代吲哚酮骨架的芳胺化合物。本发明方法操作简便，收率良好，化学选择性择性好；反应后处理简单，体系中没有副产物生成；适用底物范围广，原料均为工业化、廉价易得的产品，无污染；并且官能团兼容性高，对映选择性优秀。

Diphosphinliganden

Manganese based complexes and uses thereof for homogeneous catalysis

一种拆分外消旋面手性环芳烷磺酰亚胺类化合物的方法

本发明提供一种拆分外消旋面手性环芳烷磺酰亚胺类化合物的方法，所述方法以式I所示的环芳烷磺酰亚胺类化合物为底物，进行催化还原反应，得到面手性环芳烷磺酰亚胺类化合物(对映体过量可达92.1％)和面手性环芳烷磺酰胺类化合物(对映体过量可达93.0％，非对映体比例可达>20:1)，拆分系数可达到s＝80.2；催化还原反应的催化剂是镍的手性双膦配合物，由镍盐与手性双膦配体原位络合而成；本发明可以实现催化拆分，操作简单易行，催化剂商业可得，条件温和，能耗低，环境友好且拆分系数高，产率好。

螺双二氢苯并噻咯双膦类化合物、其制备方法及应用

本发明公开了一种螺双二氢苯并噻咯双膦类化合物、其制备方法及应用。本发明具体公开了如式(I)所示的螺双二氢苯并噻咯双膦类化合物，其可用于催化C sp3 ‑H芳基化反应和烯烃氢甲酰化反应，具有如下一个或多个优点：催化活性高；产物对映选择性高。

Manganese based complexes and uses thereof for homogeneous catalysis

The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2)C—C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

超交联聚合物负载金属催化剂用于合成环碳酸酯中的应用

本发明提供了一种超交联聚合物负载金属催化剂用于合成环碳酸酯中的应用。该超交联聚合物基金属催化剂由多孔超交联聚合物负载金属制得；所述多孔超交联聚合物由以芳基化合物为合成单体、二甲氧基甲烷为交联剂和无水三氯化铁为催化剂，通过傅‑克烷基化反应制得；所述芳基化合物的结构式为如式L 1 ‑L 5 中的一种。本发明提供的超交联聚合物催化剂的催化效率高，且反应过程中无需另加入溶剂和TBAB等助催化剂，方便产物的分离提纯。使用本发明提供的催化剂催化CO 2 与环氧丙烷合成环碳酸酯，产率最优能够达到99％。同时，使用该超交联聚合物催化剂可以在低CO 2 浓度下催化反应的进行，为工业化的应用提供了技术支持。

一种氮烷基化不饱和多元环β-氨基腈的合成方法

本发明属于β‑氨基腈类及其衍生物的合成技术领域，具体涉及一种氮烷基化不饱和多元环β‑氨基腈的合成方法。本发明在惰性气体保护下，以廉价的工业级原料腈类化合物和伯醇为原料，加入碱和有机钌催化剂，利用一锅法来实现腈类化合物关环反应、伯醇脱氢偶联反应、以及碳‑氮双键的还原反应合成得到氮烷基化不饱和多元环(五元环、六元环)β‑氨基腈，反应体系简单，操作简便，反应条件温和，反应底物具有良好的适用性，制得的氮烷基化不饱和多元环β‑氨基腈具有收率好、化学选择性高的特点。此外，本发明还克服了底物范围有限、原料试剂昂贵、反应体系复杂、合成步骤冗长等缺陷，反应经济效益较高，绿色环保，反应后处理简单。

Funktionalisierte ferrocenyldiphospine, verfahren zu ihrer herstellung und ihre verwendung

Phosphinverbindungen, übergangsmetallkomlexe mit den verbindungen, die als liganden darin enthalten sind, und asymmetrische synthesekatalysatoren mit diesen komplexen

基於錳的配合物及其在均相催化中的用途

酯化合物之製造方法

一種藉由使醋酸乙烯酯、式(1)所示的1級或2級醇與一氧化碳反應而生成式(2)所示的第1酯化合物，藉由使第1酯化合物與醇反應而生成式(3)所示的乳酸酯與式(4)所示的醋酸酯之製造方法。

Method for producing ester compound

What is provided is a production method in which a vinyl acetate is reacted with a primary or secondary alcohol represented by Formula (1) and carbon monoxide to produce a first ester compound represented by Formula (2), and the first ester compound is reacted with an alcohol to produce a lactic acid ester represented by Formula (3) and an acetic acid ester represented by Formula (4).        R¹OH     (1)

Method for producing ester compound

What is provided is a production method in which a vinyl acetate is reacted with a primary or secondary alcohol represented by Formula (1) and carbon monoxide to produce a first ester compound represented by Formula (2), and the first ester compound is reacted with an alcohol to produce a lactic acid ester represented by Formula (3) and an acetic acid ester represented by Formula (4).

エステル化合物の製造方法

酢酸ビニルと式（１）で示される１級または２級アルコールと一酸化炭素とを反応させることにより式（２）で示される第１エステル化合物を生成させ、第１エステル化合物とアルコールとを反応させることにより式（３）で表される乳酸エステルと式（４）で表される酢酸エステルとを生成させる製造方法とする。

Herstellung optisch aktiver phospholane

Manganese based complexes and uses thereof for homogeneous catalysis

The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

Manganese based complexes and uses thereof for homogeneous catalysis

The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C—C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a hydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

Manganese based complexes and uses thereof for homogeneous catalysis

The present invention relates to novel manganese complexes and their use, inter alia , for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

超交联聚合物负载金属催化剂用于合成环碳酸酯中的应用

本发明提供了一种超交联聚合物负载金属催化剂用于合成环碳酸酯中的应用。该超交联聚合物基金属催化剂由多孔超交联聚合物负载金属制得；所述多孔超交联聚合物由以芳基化合物为合成单体、二甲氧基甲烷为交联剂和无水三氯化铁为催化剂，通过傅‑克烷基化反应制得；所述芳基化合物的结构式为如式L 1 ‑L 5 中的一种。本发明提供的超交联聚合物催化剂的催化效率高，且反应过程中无需另加入溶剂和TBAB等助催化剂，方便产物的分离提纯。使用本发明提供的催化剂催化CO 2 与环氧丙烷合成环碳酸酯，产率最优能够达到99％。同时，使用该超交联聚合物催化剂可以在低CO 2 浓度下催化反应的进行，为工业化的应用提供了技术支持。

エステル化合物の製造方法

Preparation method for tetra-substituted allenoic acid compound based on palladium catalytic system

Disclosed in the present invention is a preparation method for a tetra-substituted allenoic acid compound based on a palladium catalytic system, that is, a highly optically active allenoic acid compound having axial chirality is directly constructed in one step by reacting tertiary propargyl alcohol, carbon monoxide and water in an organic solvent under the action of a palladium catalyst, a chiral bisphosphine ligand, an organophosphoric acid, and an organic additive, and the theoretical yield can reach 100%. The method of the present invention is simple to operate, the raw materials and reagents are readily available, the reaction conditions are mild, the substrate universality is wide, the functional group compatibility is good, the reaction has high enantioselectivity (77%˜96% ee), and the reaction is well compatible with complex natural products or substrates of a drug molecular skeleton. The highly optically active allenoic acid compound obtained by the present invention can be used as an important intermediate for constructing a γ-butyrolactone compound containing a tetra-substituted chiral quaternary carbon center, tetra-substituted allenol, tetra-substituted allenal, tetra-substituted allenyl ketone, tetra-substituted allenami de and other compounds.

Method for producing ester compound

一种氮烷基化不饱和多元环β-氨基腈的合成方法

本发明属于β‑氨基腈类及其衍生物的合成技术领域，具体涉及一种氮烷基化不饱和多元环β‑氨基腈的合成方法。本发明在惰性气体保护下，以廉价的工业级原料腈类化合物和伯醇为原料，加入碱和有机钌催化剂，利用一锅法来实现腈类化合物关环反应、伯醇脱氢偶联反应、以及碳‑氮双键的还原反应合成得到氮烷基化不饱和多元环(五元环、六元环)β‑氨基腈，反应体系简单，操作简便，反应条件温和，反应底物具有良好的适用性，制得的氮烷基化不饱和多元环β‑氨基腈具有收率好、化学选择性高的特点。此外，本发明还克服了底物范围有限、原料试剂昂贵、反应体系复杂、合成步骤冗长等缺陷，反应经济效益较高，绿色环保，反应后处理简单。

一种钴催化环n-磺酰基亚胺的对映选择性还原（杂）芳基化方法及应用

本发明公开了一种钴催化环N‑磺酰基亚胺的对映选择性还原(杂)芳基化方法及应用。本发明所述方法是以环N‑磺酰基亚胺和芳基或杂芳基卤化物为原料，通过钴催化环N‑磺酰基亚胺的对映选择性还原芳基化或杂芳基化得到。本发明首次在还原条件下探索了钴催化的芳基和杂芳基卤化物对环N‑磺酰基亚胺的对映选择性加成，避免了传统策略中预成型有机金属试剂的使用，弥补了现有技术的空缺。

一种乙烯选择性齐聚催化体系及其应用

本发明公开了一种乙烯选择性齐聚催化体系及其应用，该催化剂体系包括配体a、过渡金属化合物b以及活化剂c；其中过渡金属化合物b为IVB～VIII族的金属化合物；活化剂c为含有IIIA族金属的化合物；配体a的结构通式如式(I)所示： 其中，R 1 、R 2 相同或不同，分别独立地选自氢、烷基或芳基；或者R 1 和R 2 与P原子形成环状结构。本发明的催化剂体系稳定性高、耐温性好、催化活性和目标产物选择性高，同时可通过工艺条件的控制灵活切换三聚/四聚催化性能。

超交联聚合物负载金属催化剂用于合成环碳酸酯中的应用

本发明提供了一种超交联聚合物负载金属催化剂用于合成环碳酸酯中的应用。该超交联聚合物基金属催化剂由多孔超交联聚合物负载金属制得；所述多孔超交联聚合物由以芳基化合物为合成单体、二甲氧基甲烷为交联剂和无水三氯化铁为催化剂，通过傅‑克烷基化反应制得；所述芳基化合物的结构式为如式L 1 ‑L 5 中的一种。本发明提供的超交联聚合物催化剂的催化效率高，且反应过程中无需另加入溶剂和TBAB等助催化剂，方便产物的分离提纯。使用本发明提供的催化剂催化CO 2 与环氧丙烷合成环碳酸酯，产率最优能够达到99％。同时，使用该超交联聚合物催化剂可以在低CO 2 浓度下催化反应的进行，为工业化的应用提供了技术支持。

酯化合物的制造方法

本发明提供一种制造方法，其中通过使乙酸乙烯酯、式(1)表示的伯醇或仲醇、和一氧化碳进行反应来生成式(2)表示的第一酯化合物，并通过使第一酯化合物和醇进行反应来生成式(3)表示的乳酸酯和式(4)表示的乙酸酯。R 1 OH…(1)