Total synthesis of Pumiliotoxin B (Overman):
| Reference: | Lin, N.-H.; Overman, L. E.; Rabinowitz, M. H.; Robinson, L. A.; Sharp, M. J.; Zablock, J.. J. Am. Chem. Soc. 1996, 118, 9062. DOI |
| Reactions: | CarboxAcid → Alkyl-OH • O-SiPh2tBu → O-H • Corey-Fuchs • Wittig-ketomethyl → Enone • Fritsch-Buttenberg-Wiechell • CarboxAmide enolate(Evans)+Alkyl-X • Allyl-X+Enolate (asym) • Al-Alkynyl+Epoxide • Epoxide+Al-R • Li-R → Al-R • Vinyl-I → Vinyl-H • CarboxAmide(Evans) → CarboxAcid • Mannich carboiodination • Amine-6 • Bicyclo(430)-aza • Enone → Allyl-OH • Diol-1,2 → Ketal • Alkyl-OH → Aldehyde • Alkene cleavage • Lemieux-Johnson oxidation • CompOx-Alkene/Alkene+OsO4 • Li/I → Li-Vinyl • Dehydrohalogenation → Alkyne • |
| Reagents: | PPh3=C(Me)-C(O)R • Chiral auxiliary (amide-Evans) • LiN(SiMe3)2 • Allyl-I • H2O2, NaOH • AlH4-Li+ • DMSO, CF3CO2H (Moffat) • PPh3=CBr2 • OsO4, NMO • AlHiBu2 • Fluoride, R4N+ • Me2C(OMe)2 • BuLi(n) • Epoxide • Hydroxide, barium • BuLi(tert) • Chloride, ammonium • AlEt2-Cl • Iodide, sodium • Formaldehyde • TsOH·Py • PPh3, CBr4 • |