Andrew ratz Daphniphyllum Alkaloids Evans Group Seminar, June 1993 Synthesis of ()-Secodaphniphylline Rationale for Stereoselectivity in Michael Additions COmE COX OBn 2. HgSOA COmE Lo. 3.(COCa CHCh 28 90%ee 器e 43% overall 32D0712/110011:47AMAndrew Ratz Daphniphyllum Alkaloids Evans Group Seminar, June 1993 + 99.6% ee NaCN, DMSO 150°C 43% overall 92% ee 90% ee 1. separate 2. KOH EtOH 3. (COCl)2, CH2Cl2 31% 1. RuCl3, NaIO4 2. CH2N2 1 : 5 HgSO4 H2SO4 95% KAPA 1,3-diaminoprop. 87% 92% ee LAH Darvon Alc. 93% 1. Weinreb 2. Synthesis of (-)-Secodaphniphylline + + J. Org. Chem. 1980, 45, 582 Tet. Lett. 1981, 22, 4171 J. Org. Chem. 1981, 46, 3936 Tet Lett. 1967, 8, 215 HN Me iPr O O O Me Me O O HO2C Me Me Me Me Me Me O O O Me Me OH O O Me Me Me Me Me Me O O OH O O Me Me Me CH2OH HOCH2 Me O O O O Me MeO2C Me CO2Me Me Me O O O OMe Me COCl HN Me iPr HN Me iPr O O O Me Me MeO2C Me Me O O O iPr HN Me COX Me Me O O CO2Me iPr HN Me Me Li MeO OLi 1. LDA, THF 2. 3. Interference with Li cluster ?? Tet Lett 1986, 27, 959 J. Org. Chem. 1990, 55, 132 Topics in Stereochemistry 1989, 227 Rationale for Stereoselectivity in Michael Additions N OMe H O O Li BnO N OBn O LiO OMe H Me I Me Me N OBn O CO2Me N Me Me Me OBn MeO2C O OMe N O OBn H H Me Me O Li N MeO O H BnO O Me Me Li O N MeO2C OBn Me Me Me N Me Me Me OBn MeO2C O Me Me Me Me H 32D-07 12/11/00 11:47 AM