Total synthesis of Pironetin:
| Reference: | Dias, L. C.; Oliveira, L. G.; Sousa, M. A. Org. Lett. 2003, 5, 265. DOI |
| Reactions: | O-H → O-SiMe2tBu • CompNu-O-H/O-H+RSO2X • O-PMB → O-H • CarboxAmide(Weinreb) → Aldehyde • Aldol-B-Evans • CarboxAmide enolate+Aldehyde (asym) • HWE → EnoateEster-cis • Alkyne → Ene-trans • CompRed-Alkyne/Bn-OR+M° • Aldol-B-Evans • CarboxAmide enolate+Aldehyde (asym) • Li-Alkynyl+Alkyl-X • Li/H → Li-Alkynyl • Aldol-B-Evans • CarboxAmide enolate+Aldehyde (asym) • CarboxAmide(Evans) → Alkyl-OH • Alkyl-OH → Aldehyde • O-H → O-SO2Ar • O-H → O-Me • O-H → O-SiMe2tBu • CarboxAmide(Evans) → Alkyl-OH • Alkyl-OH → Aldehyde • O-SiMe2tBu → O-H • Lactone-6 • CarboxAmide(Evans) → CarboxAmide(Weinreb) • Li-Alkynyl+Alkyl-X • |
| Reagents: | NMe(OMe)-AlMe2 • SiMe2tBu-OTf • AlHiBu2 • Chiral auxiliary (amide-Evans) • BH4-Li+ • TsCl, NEt3 • Me3O+ X- • Alkynyl-Li • BuLi(n) • Na°/NH3 • DMSO, (COCl)2 (Swern) • Chiral auxiliary (amide-Evans) • SiMe2tBu-OTf • BH4-Li+ • RuO4-Pr4N+, NMO • NaH • HCl, H2O • Chiral auxiliary (amide-Evans) • Chiral auxiliary (amide-Evans) • MeI • DMSO (solvent) • Chiral auxiliary (amide-Evans) • Chiral auxiliary (amide-Evans) • Lutidine • |