Total synthesis of Tubingensin A (Nicolaou) New:
| Reference: | Bian, M.; Wang, Z.; Xiong, X.; Sun, Y.; Matera, C,; Nicolaou, K, C.; Li, A. J. Am. Chem. Soc. 2012, 134, 8078–8081. DOI |
| Reactions: | O-SiMe2tBu → O-H • Ketone → EnolSilane • ConjAdd EnolSilane • Enone+EnolSilane • Mukaiyama-Michael • Aldol-Na → Enone • Robinson annulation, ketone • Cyclohexenone • Bicyclo(440) • Enone → Enol • Enone → Enone-γ-OR • Iodoetherification • Radical cyclization(Alkyl) • Ketone → EnolSilane • Mukaiyama Aldol • Aldol-Si • Aldehyde+EnolSilane • O-H → O-SiMe2tBu • Wittig-methyl • Alkyl-OH → Aldehyde • Mg-Aryl+Aldehyde • Aldehyde+Mg-R • O-H → O-C(S)SR • Alkyl-OH → Alkyl-H(2°) • Barton-McCombie reduction • N-SO2R → N-H • Acetal → Lactol • Mg-Vinyl+Aldehyde • Aldehyde+Mg-Vinyl • O-H → O-C(O)R • Allyl-X → Allyl-H • Olefin cross metathesis • O-C(O)R → O-H • Dehydrosulfonoxylation → Ene • Electrocyclic-6π • Benzene synthesis • Mg-Vinyl+Aldehyde • Aldehyde+Mg-Vinyl • O-H → O-C(O)R • Allyl-X → Allyl-H • O-C(O)R → O-H • Olefin cross metathesis • N-SO2R → N-H • |
| Reagents: | SiMe3-Cl • Iodide, sodium • NH(SiMe3)2 (HMDS) • Methyl vinyl ketone • BF3·OEt2 • NaOMe • Orthoformate • TsOH • Oxone • NIS • Vinyl-OR • HSnBu3 • AIBN • HCl, EtOH • LiN(SiMe3)2 • SiMe3-Cl • Formaldehyde • SiMe2tBu-Cl • Imidazole • PPh3=CH2 • Fluoride, R4N+ • Dess-Martin • Aryl-MgX • BuLi(n) • KN(SiMe3)2 • CS2 • HSnBu3 • AIBN • Fluoride, R4N+ • HClO4 • Vinyl-MgX • Acetic anhydride, NEt3 • Pd(PPh3)4 • AlHiBu2 • Sulfonyl chloride, methane, NEt3 • CuOTf • HClO4 • Vinyl-MgX • Acetic anhydride, NEt3 • Pd(PPh3)4 • AlHiBu2 • Fluoride, R4N+ • |