MIXTURES OF CHIRAL MONOPHOSPHORUS COMPOUNDS USED AS LIGAND SYSTEMS FOR ASYMMETRIC TRANSITION METAL CATALYSIS
(19) AUSTRALIAN PATENT OFFICE (54) Title MIXTURES OF CHIRAL MONOPHOSPHORUS COMPOUNDS USED AS LIGAND SYSTEMS FOR ASYMMETRIC TRANSITION METAL CATALYSIS (51 )6 International Patent Classification(s) B01J 031/18 C07F 009/50 C07F 015/00 C07F 019/00 CO7F009/G571 B01J 031/24 C07B 053/00 B01J 023/46 (21) (87) (30) (31) (43) (43) (71) (72) Application No: 2003269835 WIPONo: WO04/035208 (22) Application Date: 2003.09.26 Priority Data Number 102 47 633.0 (32) Date 2002.10.11 (33) Country DE Publication Date : Publication Journal Date 2004.05.04 2004.06.10 Applicant(s) STUDIENGESELLSCHAFT KOHLE MBH Inventor(s) REETZ, Manfred, T.: SELL, Thorsten; MEISWINKEL, Andreas; MEHLER, Gerlinde The invention relates to certain chiral transition metal catalysts, to the metal of which at least two structurally different monophosphorus ligands are bonded, at least one of said monophosphorus ligands being chiral. Said chiral transition metal catalysts are suitable as catalysts for use in asymmetric transition metal-catalyzed reactions, providing better enantioselectivities than in cases where only one structurally defined ligand is used. A chiral transition metal catalyst, characterized in that at least two structurally different monophosphorus ligands are bonded to the metal selected from Rh, Ir, Ru, Ni, Pd or Pt, at least one monophosphorus ligand being chiral which is selected from mono-P-compounds of the B, C or D type:
where W is carbon (C), nitrogen (N), oxygen (O), sulfur (S) or halogen (F, Cl, Br, I),
and further atoms or groups of atoms are bonded to W according to its number of free valences,
and where the radicals R1, R2, R3, R4, R5, R6, R7, R8, R1', R2', R3', R4', R5', R6', R7' and R8' are each independently selected from the group of hydrogen, halogen, saturated and unsaturated, linear and branched C1-C50 alkyl, C6-C50 aryl, C1-C50 heteroaryl, alkynyl silyl, nitro, nitrile, ester, carboxyl, carbonyl, amide, amine, hydroxyl, alkoxy, sulfide and selenide groups,
where R1, R2, R3, R4, R5, R6, R7, R8, R1', R2', R3', R4', R5', R6', R7' and R8' in turn bear further substituents or may be functionalized. A chiral transition metal catalyst as claimed in claim 1, wherein at least two monophosphorus ligands are chiral. A chiral transition metal catalyst as claimed in any of claims 1 or 2, wherein the monophosphorus ligands are phosphines, phosphites, phosphonites, phosphinites, phosphorous triamides, phosphorous monoester diamides, phosphorous diester amides, phosphonous diamides, phosphinous amides, phosphonous monoester amides, phosphorous halides, phosphorous diamide halides, thiophosphites, thiophosphorous triesters, thiophosphorous monoester diamides or thiophosphorous diesteramides. A catalyst as claimed in any of claims 1 to 3, wherein at least one achiral ligand is a monophosphorus compound of the H-T type
wherein the radicals R1, R2, R3 and R4 are each independently selected from the group of hydrogen, halogen, saturated and unsaturated, linear and branched C1-C50 alkyl, C6-C50 aryl, C1-C50 heteroaryl, alkynyl, silyl, nitro, nitrile, ester, carboxyl, carbonyl, amide and selenide groups,
where R1, R2, R3 and R4 in turn bear further substituents and may be functionalized or bridged. A catalyst as claimed in any of claims 1 to 4, wherein the chiral monophosphorus ligands used are at least two ligands of the type
where W is each independently CH3, C(CH3)3, c-C6H11 or OCH3. A process for catalytically preparing chiral organic compounds, characterized in that prochiral organic compounds are hydrogenated in the presence of a chiral transition metal catalyst as claimed in any of claims 1 to 5.