Total synthesis of Phyllanthocin New:
| Reference: | Smith, III, A. B.; Fukui, M.; Vaccaro, H. A.; Empfield, J. R. J. Am. Chem. Soc. 1991, 113, 2071-2092. DOI |
| Reactions: | Fluoride, R4N+ • Spiroketalization • Ketone → Ketal • Ketal → Ketal-α-halo • Dehydrohalogenation → EnolEther • Li/H → Li-Vinyl-OR • Aldehyde → Acetal(Me) • CarboxEster enolate+Alkyl-X • Alkyl-X+Enolate • CarboxEster → Alkyl-OH • O-H → O-Bn • Acetal → Aldehyde • Prins • Cyclohexane • O-H → O-MEM • Ozonolysis • Ketal → Enone • Allyl-OH → Enone • EnolEther → Ketal • Sulfonium ylide+Ketone • Epoxidation ylide • Corey-Chaykowsky • Ketone → EnolSilane • Ketone enolate+Me-I • Fluorodesilylation → Enolate • Ketone epimerization • O-Bn → O-H • Alkyl-OH → CarboxAcid • CarboxAcid → CarboxEster • Ketone → Alkyl-OH • O-H → O-C(O)R • |
| Reagents: | TsOH • Tribromide • KOtBu • DMSO (solvent) • BuLi(tert) • Orthoformate • CeCl3 • LiNiPr2 • HMPA (solvent) • AlH4-Li+ • KH • Benzyl-X • HCl, H2O • AlMe2-Cl • MEM-Cl • O3; PPh3 • Oxalic acid • DMSO, (COCl)2 (Swern) • NEt3 • HMPA (solvent) • ZnBr2 • Sulfonic acid, Camphor • Me2S(O)=CH2 • LiNiPr2 • SiMe3-Cl • MeI • DBU • H2, Pd • RuO4 • Diazomethane • BH4-Na+ • Me3SO+ I- • Periodate, sodium • |