Total synthesis of Jiadifenolide (Paterson):
| Reference: | Paterson, I.; Xuan, M.; Dalby, S. M. Angew. Chem. Int. Ed. 2014, 53, 7286–7289. DOI |
| Reactions: | O-H → O-SiMe2tBu • HWE → EnoateEster • Pinacol • Epoxidation, peracid • Henbest • EnoateEster → Allyl-OH • Claisen-Ireland • Enone → Allyl-OH • O-H → O-C(O)R • O-SiMe2tBu → O-H • CarboxEster → EnolBorane • O-H → O-SiEt3 • CarboxEster → Alkyl-OH • Alkyl-OH → Aldehyde • Alkyl-OH → Ketone • Aldol-BR2 → Aldol • O-SiEt3 → O-H • Radical cyclization(Ketyl) • Cyclohexane • Bicyclo(430) • Alkyl-OH → Ketone • Ketone → EnolSilane • O-H → O-SiEt3 • O-SiEt3 → O-H • EnolSilane → Ketone-α-OH • CompOx-Alkene/Alkene+OsO4 • Ketone → Alkyl-OH • CompRed-Ketone/Lactone+M-H • Alkene → Diol-1,2 • Alkyl-OH → KetoEster • Lactone-5 • |
| Reagents: | BH4-Na+, CeCl3 • Perbenzoic acid, 3-chloro • Imidazole • BF3·OEt2 • NaH • AlH4-Li+ • Acetic anhydride, DMAP • LiNiPr2 • SiMe2tBu-Cl • AlH4-Li+ • DMSO, (COCl)2 (Swern) • B(OTf)Bu2 • SiEt3-Cl • SmI2 • TsOH·Py • CrO3Cl·PyH (PCC) • SiMe3-OTf • NEt3 • OsO4, NMO • SiEt3-Cl • OsO4, NMO • RuO4-Pr4N+, NMO • HF·Py • |