D. A. Evans. M. Calter The Aza-Cope Rearrangement Chem 115 Akuammicine: Overman JOC 1985. 50. 4021 (+-6a-epipretazettine: Overman JACS 1979, 101, 1310 BnN(AIMe2)H Cu(oTf) Me 4)Phococ Swern 2)40% KOH (many ubstrates Danishefsky JACS 1982, 104, 7591 D-ring has to assume boat conformation in 32B-0911/24/931021AMD C B A E D C B A Akuammicine E-ring will not close(many substrates tried) CSA,110oC, 20 min., 100% 1)HCHO 2)TBSCl 95% 1)Ph3P=CH2, 2)40% KOH, 95% 70% + Swern, 87% 1)DIBAL-H 2)TIPSCl 3)BnN(AlMe2)H 4)PhOCOCl 47% MCPBA, 92% The last two steps tie into Danishefsky's synthesis of (±)-6a-epipretazettine. Danishefsky JACS 1982, 104, 7591. 1)HC(OMe)3, H+ 2)H3O+ 73% 1)MCPBA 2)Ms2O,MeOH 3)TBAF 15% 1)TMSOTf 2)DIBAL-H 3)PhSeCl 60% H2O2, KF, 76% + + Cu(OTf)2 94% 41% + (±)-6a-epipretazettine: Overman JACS 1979, 101, 1310. Akuammicine: Overman JOC 1985, 50, 4021. D-ring has to assume boat conformation in order for E-ring to close. D. A. Evans, M. Calter The Aza-Cope Rearrangement Chem 115 CO2Et Me Me CO2Et O HO N PhO2C Me OTIPS Bn N Bn OTIPS Me PhO2C HO N NBOC Li TMSO CN Li Me OTIPS O Bn O O BOCHN H2N HO N HN Bn OH Me Me Bn TBSO O H2N N N TBSO Bn N CO2Me N H N NR X Me H O N O O Cl2Ce SiMe2Ph Me CN SiMe2Ph O O N HO Me NC N Me O H O O SiMe2Ph N Ar SiMe2Ph OH OH SiMe2Ph Ar N Me Me N OH Me HO O O SiMe2Ph N H O Ar N Me Me HO Ar H OTMS PhSe HO OH H Ar N Me HO N H Me O O O OH 32B-09 11/24/93 10:21 AM