Total synthesis of Pumiliotoxin B (Kibayashi):
| Reference: | Aoyagi, S.; Hirashima, S.; Saito, K.; Kibayashi, C. J. Org. Chem. 2002, 67, 5517. DOI |
| Reactions: | Si-Allenyl+Ketone • Ketone+Si-R • Amine-5 • Corey-Fuchs • Cu-SiR3+Propargyl-X • Allene synthesis • Hydrostannation Alkyne • Li/I → Li-Alkyl • Li-R → Zn-R • Takai-Utimoto → Vinyl-I • Sn-Vinyl → I-Vinyl • Pd-Carboxylation • EnolTriflate → EnoateEster • Lactone-5 • Li-Alkynyl+Aldehyde • N-H → N-Allyl • Amine-6 • Bicyclo(430)-aza • Alkyl-OH → Alkyl-I • Fritsch-Buttenberg-Wiechell • Aldehyde → Alkyne • Pd/Zn-Alkyl+Vinyl-X • O-H → O-SO2Me • N-Boc → N-H • N-H → N-Boc • Lactone → Alkyl-OH • O-H → O-SiMe2tBu • O-SiMe2tBu → O-H • CompE+-Si-O/Si-O+H2O • O-SiMe2tBu → O-H • Ketal → Diol-1,2 • Allyl-OH → Allyl-Br • Appel → Br • |
| Reagents: | ZnCl2 • BuLi(tert) • BuLi(n) • Sulfonyl chloride, methane, NEt3 • CuCN • Allenyl-SiR3 • HfCl2 • Boc2O • HSnPh3 • BEt3 • NIS • Pd(OAc)2 • PPh3 • Acetic acid, trifluoro • AlHiBu2 • PPh3, CBr4 • TASF • SiMe2tBu-OTf • PPh3, I2 • Imidazole • HF·NEt3 • HCl, H2O • CHI3 • Formaldehyde • CO • Vinyl-I • Pd(PPh3)4 • PPh3=CBr2 • PPh3, CBr4 • |