B.环外传递 OLi PhCH2Br M CH2Ph H e Me Me e N Me N CH2Ph >95 C.配位型环内传递 PhCH2Br oO M Me Me NO NO PhCH PhCH2 辅基 120
B. 环外传递 C. 配位型环内传递 O N O Li Me O PhCH2 Br OoC O N O Me O PhCH2 O N O Me O PhCH2 120 1 辅基 N N Me OLi H Ph Me PhCH2 Br -60 N N O H Ph Me Me CH2 Ph N N O H Ph Me CH2 Ph Me >95 5
2.环内手性传递 A.六员环 CO2R CO2R Me co2R Me Me LDA Me Mel 95 5 CN Me CN Nc Me LDA Mel But But But 71 29
2. 环内手性传递 A. 六员环 CO2 R Me LDA MeI CO2 R Me Me CO2 R Me Me 95 5 Bu t CN LDA MeI Bu t Me CN Bu t NC Me 71 29
OM RX R R R R RX anti: syn n'C4Hg M 88:12 CH2=CH Mel 75:25 CH3 CH2=CHCH2 Br 89:11
OM R' R''X O R'' R' O R'' R' R' R''X anti:syn n - C4 H9 MeI CH2 =CH- MeI CH3 CH2 =CHCH2 Br 88:12 75:25 89:11
B.五员环 LDA B Only product Ph Ph Ph LDA Me Me oMe Mel M oMe 93
B. 五员环 O O LDA Br O O Only product O N Ph Me LDA MeI O N Ph Me Me O N Ph Me Me 93 7
C.降冰片体系 LDA CO,R Me CO2R M H Me CO2R R=H74 26 R=Me 97 3 Me LDA. HMPT Only Product CO2Et Br CO2Et OAC OAC
C. 降冰片体系 H CO2 R LDA MeI Me CO2 R Me CO2 R R=H 74 26 R=Me 97 3 Me CO2 Et LDA, HMPT Br OAc CO2 Et OAc Only Product