Total synthesis of ACRL Toxin IIIb:
| Reference: | Munchhof, M. J.; Heathcock, C. H. J. Org. Chem. 1994, 59, 7566. DOI |
| Reactions: | CarboxAmide(Evans) → CarboxEster • O-H → O-CPh3 • Sulfide → Sulfoxide • O-THP → O-H • CarboxAcid → CarboxEster • O-SiMe2tBu → O-H • CarboxAmide(Weinreb)+Li-R • Li-Vinyl+CarboxAmide • Aldol-B-Evans • CarboxAmide enolate+Aldehyde (asym) • 2,3-Sigmatropic Sulfoxide • Sulfide → Sulfoxide • Lactone enolate+Aldehyde • Aldol-Li → Aldol • Lactone-6 • CarboxAcid → CarboxAmide(Weinreb) • CarboxAmide(Evans) → CarboxEster • Claisen-Ireland • O-H → O-CPh3 • O-H → O-C(O)R • Luche reduction • Enone → Allyl-OH • O-H → O-SiMe2tBu • O-CPh3 → O-H • Enol → EnolEther • Ketone → Alkyl-OH • Alkyl-OH → Aldehyde • Alkyl-OH → Ketone • CarboxEster → Alkyl-OH • |
| Reagents: | Chiral auxiliary (amide-Evans) • LiOCH2Ph • AlHiBu2 • Ph3CCl • O=C(Imid)2 • Vinyl-Li • BH4-Na+, CeCl3 • Perbenzoic acid, 3-chloro • P(OMe)3 • SiMe2tBu-OTf • ZnBr2 • DMSO, Py·SO3 (Parikh-Doering) • Dess-Martin • Acetic acid • BH(sBu3)-Li+ • Diazomethane • HF·Py • Chiral auxiliary (amide-Evans) • DMAP • NHMe(OMe) • LiNiPr2, HMPA • SiMe2tBu-Cl • HMPA (solvent) • |