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Total synthesis of Hemibrevetoxin B (Part 1) (Holton):
| Reference: | Zakarian, A.; Batch, A.; Holton, R. A.. J. Am. Chem. Soc. 2003, 125, 7822-7823. DOI (Part 2) |
| Reactions: | Aldehyde → Alkyl-OH • CarboxEster enolate+Alkyl-X • Allyl-X+Enolate • Alkyl-OH → Alkyl-I • Lemieux-Johnson oxidation • Alkene cleavage • Lactone-6 • Diol-1,2 → Stannadioxolane • O-SnR3 → O-CPh3 • CompNu-O-H/O-H+R-X • O-H → O-Alkyl • Lactone-6 • O-CPh3 → O-H • Henbest • CompOx-Alkene/Enoate+Peracid • EnoateEster → Allyl-OH • Epoxide reduction • Epoxidation, peracid • CompOx-Alkene/Enoate+Peracid • Furst-Plattner diaxial • Sn-Allyl+Allyl-X • Allyl-X+Sn-R • Hydroboration → Alkyl-OH • Diol-1,3 → Acetal • O-H → O-MOM • Alkyne Hydrosilylation • Cu-SiR3+Alkyne • Li-Alkynyl+Alkyl-X • Li/H → Li-Alkynyl • Alkyl-X+Li-R • Si-Vinyl → I-Vinyl • Acetal → Diol-1,3 • O-Bn → O-H • O-H → O-Tf • O-H → O-SiEt3 • CarboxEster → CarboxAcid • Iodolactonization • Lactone-6 • Pd/Zn-Alkyl+Vinyl-X • Epoxidation via halohydrin • CarboxEster → CarboxAcid • O-H → O-SiiPr3 • Vinyl-I → Vinyl-Zn • CarboxEster → CarboxAcid • Diol-1,3 → Acetal • |
| Reagents: | SnBu2(O) • NaH • Sulfonic acid, Camphor • LiNiPr2 • OsO4, NaIO4 • BH3CN-Na+ • PPh3, I2 • Allyl-I • Bromoacetate • Allyl-SnR3 • BF3·OEt2 • NaOMe • Perbenzoic acid, 3-chloro • Sulfonic acid, Camphor • AlHiBu2 • AlH4-Li+ • BH3·SMe2 • Sulfonic acid, Camphor • Chloromethyl ether • Allyl-SnR3 • Acrylate • BF3·OEt2 • Li°/NH3 • Tf2O • CuCN • NIS • Alkynyl-Li • DMPU (solvent) • SiEt3-OTf • Hydroxide, lithium • NIS • SiiPr3-OTf • NaOMe • Lutidine • Zn° • PdCl2(dppf) • Lutidine • |