Andrew ratz Daphniphyllum Alkaloids Evans Group Seminar, June 1993 Synthesis of Methyl Homosecodaphnipyllate The vollhardt "ammonia"incident 3.HcH2o100% 1.LAH96% OBn PrT LMel 28Cm5器4 978.17.476. 32D0512/110011:36AMAndrew Ratz Daphniphyllum Alkaloids Evans Group Seminar, June 1993 J. Org Chem. 1989, 54, 1215. Tet. Lett. 1986, 27, 959. Top. Stereochem. 1990, 20, 87. + + 4% 87% 1. DIBAL 83% 2. KOH, H2O, 95°C 3. HCl,H2O 100% 8% 1. LAH 96% 2. Swern 1. NH3 2. AcOH, NH4OAc 70°C 82-95% 1. H2, Pd/C 2. Jones 3. MeOH, H+ Synthesis of Methyl Homosecodaphnipyllate Me I Me Me MeO2C OHC Me N OBn O Me Me OBn OHC iPr HN Me N Me Me Me OBn MeO2C O O N MeO2C OBn Me Me Me N Me Me Me OBn MeO2C O O Me Me Me O R CO2Me HN Me OR LDA, THF -78°C to 25°C Angew. Chem. Int. Ed. Engl. 1978, 17, 476. J. Org. Chem. 1990, 57, 2544. The Vollhardt "Ammonia" Incident 1. MeNH2 2. HOAc, NH4OAc 75% + + + + OHC Me Me Me OBn OHC HN Me OBn Me Me OBn N N Me OBn Me Me Me CH3 CH3 H N OBn N Me Me OBn H 32D-05 12/11/00 11:36 AM