190851-52-6Relevant academic research and scientific papers
Asymmetric synthesis of (S,S)-(+)-1,1′-bis-(methyl-phenyl-phosphino) ferrocene
Kaloun,Merdes,Genet,Uziel,Juge
, p. 455 - 463 (2007/10/03)
The asymmetric synthesis of 1,1′-bis-(methyl-phenyl-phosphino) ferrocene 1 is described using the oxazaphospholidine borane complex 5 as synthon. Two strategies were investigated, based either on P-C bond formation by ring opening of complex 5 with the 1,1′-dilithio ferrocene 10, or on homocoupling of the cyclopentadienyl-methyl-phenyl-phosphine borane 2 anion with FeCl2. The first leads to a diastereomeric mixture of the diphosphine 1 in a 55:45 ratio, and the low stereoselectivity is explained by the steric hindrance of the ferrocene dianion. In the second strategy, the (R)-cyclopentadienyl phosphine borane 2 (85% ee) was prepared by the reaction of CpNa with the optically active chlorophosphine borane 14, derived from the aminophosphine borane 6a. The coupling of 2 leads to the 1,1′-diphosphino ferrocene borane 13, which is obtained diastereomerically pure by recrystallization, then decomplexed to the corresponding (S,S)-diphosphine 1.
