(±)- Hibiscone c hv, uranium glas hexane. rt 24h 60% 15:1.0 Four steps TSOH, C6H6 Hibiscone c Smith, A.B., Ill, et al J. Am. Chem. Soc. 1982. 104, 5568 Smith, A.B., Ill, et al J. Am. Chem 1984.106.2115 Studies toward Perhydrohistrionicotoxin n-CaHg Perhydrohistrionicotoxin hv, uranium glass, CAHg n-C4Hg Three steps CAHg Meoh NaOAc rt2 d Photoadduct not 3)AC2O, DMAP Smith, A.B., Ill, et al. J. Org. Chem. 1984, 49, 832. 36A-07 handout3/31/001:36PM(±)-Hibiscone C Smith, A.B., III, et al. J. Am. Chem. Soc. 1984, 106, 2115. EtO O i-Pr O i-Pr H Six steps 60% O i-Pr O i-Pr H H hν, uranium glass, hexane, rt, 24h 60% O O i-Pr H O3; Ph3P TsOH, C6H6 50% Four steps 7% O O i-Pr H O Me O i-Pr H CHO O 1.5 : 1.0 Not isolated Smith, A.B., III, et al. J. Am. Chem. Soc. 1982, 104, 5568. Hibiscone C Studies toward Perhydrohistrionicotoxin Smith, A.B., III, et al. J. Org. Chem. 1984, 49, 832. O n-C4H9 OEt O Three steps n-C4H9 42% O n-C4H9 1) NaBH4 2) O3; Ph3P 3) Ac2O, DMAP OAc O n-C4H9 CHO OAc O n-C4H9 CHO hν, uranium glass, MeOH,NaOAc rt, 2 d Photoadduct not isolable 9% 17% OAc O n-C4H9 H Wilkinson's catalyst OH n-C4H9 H H N n-C5H11 Perhydrohistrionicotoxin 36A-07-Handout 3/31/00 1:36 PM