Total synthesis of Hispidospermidine:
| Reference: | Frontier, A. J.; Raghavan, S.; Danishevsky, S. J. J. Am. Chem. Soc. 2000, 122, 6151. DOI |
| Reactions: | Si-Alkynyl → H-Alkynyl • CompOx-Enol/Alkene+Peracid • Alkyl-OH → Ketone-1,2-di • O-H → O-SiEt3 • Cu-Me+Enone • Enone+Ketone enolate • ConjAdd-Michael • CompE+-Enone/Alkyne+Cu-R • ConjAdd Cu-Me • Li-Dithiane+Alkyl-X • Alkyl-X+Li-R • Ketone+Mg-Alkyl • Mg-Alkyl+Ketone • Reductive amination, B-H • Aldol-Na → Enone • Cyclopentenone • Ketone → Ketone-α-OR • EnolSilane+peracid • Rubottom oxidation • ConjReduct-Silylation • ConjReduct Enone • Ketone-α-OR → Ketone-1,2-di • Ketone-1,2-di • Si-Vinyl → H-Vinyl • Hg-Vinyl → H-Vinyl • Robinson annulation, Stork • Ketone enolate+Enone • Cyclohexenone • Bicyclo(430) • Carbomercuration Alkyne • EnolSilane+Carbonium • Cyclohexane • Bicyclo(331) • Li/H → Li-Dithiane • Ketal(thio) → Ketone • Enone → EnolSilane • Ketone → Alkyl-OH • CompRed-Ketone/Ketone+M-H • O-SiEt3 → O-H • Ether-5 • Jones oxidation • Diol-1,2 → Ketone-α-OR • |
| Reagents: | BuLi(n) • Ceric ammonium nitrate • Hydroxide, sodium • Me-Cuprate • Vinyl-SiR3 • Methyl vinyl ketone • Iodide, sodium • Li°/NH3 • SiEt3-OTf • Perbenzoic acid, 3-chloro • Fluoride, R4N+ • DMSO, (COCl)2 (Swern) • BH4-Na+ • SiEt3-OTf • Me-MgI • HCl, H2O • CrO3, H2SO4 (Jones) • TsOH·Py • Alkyl-MgX • Cr2O7·2PyH (PDC) • BH3CN-Na+ • Hydroxide, potassium • LiN(SiMe3)2 • HgCl2 • SiMe3-Cl • HCl, H2O • NEt3 • |