Overman: Synthesis of trans-Kumausyne 1. n-Buu, NH4Cl, 98% 3. ACzO, pyr, 92% HF-pyr,100% trans-Kumausyne JAcs,191,113.5378 verman:Magellanine Synthesis Da(cat ) NalO Sncl (1.1 equiv) HzC2,-78→-23℃C 8 OTES 1. LDA TMSCL, THF, -78C. 85% 2. LiMe Cu, TMEDA, TMSCI 32C-103/189910:41PM JAcs,1993,115,2992Overman: Magellanine Synthesis JACS, 1993, 115, 2992 TESO CH(OMe)2 O OMe H SnCl4, (1.1 equiv.) CH2Cl2, -78 → -23 °C 57% N O OMe H 1. OsO4 (cat.), NaIO4 dioxane-H2O, rt 2. Ph2CHNH3Cl NaBH3CN i-PrOH, rt, 60% CHPh2 1. Cl3SiMe, NaI MeCN, 80 °C 2. TBSCl, imidazole DMF, rt, 76% 3. H2, Pd(OH)2, EtOAc 4. (BOC)2O, Et3N DMAP, 89% N O H Me BOC N O Me OH H (-)-Magellanine OTBS OTES O + R 1. LDA, TMSCl, THF, -78 °C, 85% 2. LiMe2Cu, TMEDA, TMSCl -78 → -23 °C Pd(OAc)2, MeCN, CF3CO2H Overman: Synthesis of trans-Kumausyne JACS, 1991, 113, 5378 O AcO Et Br trans-Kumausyne O HO Et OTBS H O 1. TMSOTf, Et3N 2. Pd(OAc)2, 53% 3. O TMSO Et OTBS - 100 °C → 0 °C 88% Cl Cl 1. n-BuLi, NH4Cl, 98% 2. citric acid, MeOH 3. Ac2O, pyr., 92% (EtO)2 P Li O Cl Cl O AcO Et OTBS 1. HF-pyr., 100% 2. PPh3, CBr4 2,6-di-t-butyl pyridine benzene, 40 °C, 40% trans-Kumausyne 32C-10 3/18/99 10:41 PM