Preparation of asymmetrically substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation

Asym. substituted biaryldiphosphine ligands I (R1 = C1-6-alkyl or C3-10-cycloalkyl optionally substituted with one or more halogen atoms; R2 and R3 are equal and are C5-10-cycloalkyl or C1-6-alkyl, or R2 is C5-10-cycloalkyl or C1-6-alkyl, and R3 is aryl optionally substituted with one or more substituents selected from the group consisting of halogen atoms, nitro, amino, C1-6-alkyl, C1-6-alkoxy and di-C1-6-alkylamino groups, and each C1-6-alkyl, C1-6-alkoxy, di-C1-6-alkylamino and C5-10-cycloalkyl group in R2 and R3 optionally being substituted with one or more halogen atoms, from 2,2',6,6'-tetra-bromobiphenyl) were prepd. by a sequence of bromine-metal exchanges and subsequent reactions. Thus, lithiation of 2',6-dibromo-2-methoxy-1,1'-biphenyl (prepn. given) with BuLi followed by phosphination with chlorodicyclohexylphosphine in THF gave 74% title compd., 2',6-bis(dicyclohexylphosphino)-2-methoxy-1,1'-biphenyl (ligand 1). RuCl3/(-)ligand 1 catalyzed enantioselective hydrogenation of Et acetoacetate gave (R)-Et 3-hydroxybutyrate. [on SciFinder (R)]


Year:
2006
Publisher:
(Lonza AG, Switz.).
Keywords:
Note:
CAN 144:129105
29-7
Organometallic and Organometalloidal Compounds
Patent
written in English.
20060112
10049-08-8 (Ruthenium trichloride); 35138-22-8; 37366-09-9; 52462-29-0 Role: CAT (Catalyst use), USES (Uses) (prepn. of asym. substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation); 871707-42-5P; 871707-44-7P Role: CAT (Catalyst use), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), USES (Uses), RACT (Reactant or reagent) (prepn. of asym. substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation); 871915-66-1P; 871915-67-2P; 871915-68-3P; 871915-69-4P Role: CAT (Catalyst use), SPN (Synthetic preparation), PREP (Preparation), USES (Uses) (prepn. of asym. substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation); 100-46-9 (Benzylamine); 108-36-1 (1,3-Dibromobenzene); 141-97-9 (Ethyl acetoacetate); 617-52-7 (Dimethyl itaconate); 638-07-3 (Ethyl 4-chloro-3-oxobutyrate); 1079-66-9 (Chlorodiphenylphosphine); 5469-45-4; 14428-98-9; 16523-54-9 (Chlorodicyclohexylphosphine); 52386-78-4 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of asym. substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation); 19821-80-8P (1,3-Dibromo-2-iodobenzene); 97038-96-5P; 507241-82-9P; 873110-78-2P; 873110-79-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of asym. substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation); 152578-86-4 Role: RGT (Reagent), RACT (Reactant or reagent) (prepn. of asym. substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation); 2018-61-3P; 3618-96-0P; 17480-69-2P; 22644-27-5P; 24915-95-5P; 86728-85-0P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of asym. substituted biaryldiphosphines and their use as cocatalysts for transition metal catalyzed enantioselective hydrogenation)
A1
EP
2004-14908
20040625
Patent number(s):
Laboratories:




 Record created 2006-03-03, last modified 2018-01-27


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