有机立体化学-Slid-8

8.4 不对称催化合成（手性放大）

Cat*AB*

8.4.1 不对称催化氢化 碳－碳双键氢化

CO2H+HRh / L*CO2H2*PhNHCOCH3PhNHCOCH3

L* e e (%)

____________________________________ DIOP 85 BINAP 100

DuPHOS

99

42

手性膦配体

HOPPhMePPh22PPPPOPPh2HMePPh2 DIOP CHIAPHOS DuPHOS Penn-PHOS(Kagan, 1971)(Bosnich, 1977)(Burk, 1990)(Zhang, 1998)OMeNPhPCy2PPhMeOPPhMeOPPh22MePhMeOPPhMeOPPh2FePPh22PPhNOMe JOSIPHOS BINAPMeO-BIPHEP P-PHOS(Togni, 1994)(Noyori, 1980)(Schmid, 1991)(Chan, 2000)

43

＋PhCO2MePSRhINHAcPSK1KOe4PhC2MNHAcHCH2Ph＋PCCO2MeK3RhIIINHPOSPh＋PRhICO2MePONHH2K2HPh＋PRhIIICO2MePHNHO44

机理

不对称催化氢化工业应用

不对称催化第一个工业化例子, L-Dopa (Monsanto, 1975)

oMeOCOH2 (3 bar) / 50C2HRh(COD)2BF4 / L*AcONHAcHOCO-2HONH+3L -Dopa

MeOCO2HAcONHAc95% eeH3COPPOCH3(R,R)-DIPAMP45