Total synthesis of De-A-Quassimarin:
| Reference: | Kawabata, T.; Grieco, P. A.; Sham, H.-L.; Kim, H.; Jaw, J. Y.; Tu, S. J. Org. Chem. 1987, 52, 3346 DOI |
| Reactions: | Ketone → EnolSilane • Ketone → Ketone-α-SeR • Ketone → EnolSilane • EnolSilane → Ketone-α-Halo • O-H → O-SiMe2tBu • O-SiMe2tBu → O-H • Alkyl-OH → Aldehyde • Ketone → EnolSilane • Saegusa oxidation • Ketone → Enone • O-H → O-MOM • O-MOM → O-H • Allylic oxidation → Enone • Enone enolate+Alkyl-X • Alkyl-X+Enolate • ConjReduct Enone • Selenoxide-Ei → Enone • ConjAdd Cu-Vinyl • Cu-Vinyl+Enone • Ketone → Ketone-α-Halo • EnolSilane → Ketone-α-Halo • Ketone → Alkene • Shapiro reaction • Epoxidation, peracid • Ketal(thio) → CH2 • Ketone → CH2 • Iodolactonization • Lactone-6 • Alkyl-X → Alkyl-H(2°) • Radical reduction(C-I) • Lactone → Lactone-α-OR • CarboxEster enolate oxidation • Ether-5 • Bicyclo(321)-oxa • Ketone-α-Halo → Ketone-α-OR • Enone → Ketal(thio) • CarboxEster → CarboxAcid • O-H → O-MOM • Hydroboration → Alkyl-OH • O-H → O-Me • Aldehyde → CarboxAcid • Ketal → Ketone • Lactone-6 • O-H → O-MOM • Diol-1,2 → Ketone-α-OR • Ketone → Hydrazone • |
| Reagents: | MeI • CrO3·Py2 (Collins) • LiNiPr2 • MeI • Li°/NH3 • NH(SiMe3)2 (HMDS) • SiMe3-I • SePh-Cl • H2O2 • Vinyl-Li • CuI·PBu3 • NH(SiMe3)2 (HMDS) • SiMe3-I • NBS • DMF (solvent) • BH3·THF • H2O2, NaOH • SiMe2tBu-Cl • CrO3·Py2 (Collins) • Fluoride, R4N+ • Hydrazine, tosyl • LiNiPr2 • CrO3·Py2 (Collins) • Ag2O • TsOH • Chloromethyl ether • NH(SiMe3)2 (HMDS) • SiMe3-I • Pd(OAc)2 • Thiol, (CH2)2-SH • BF3·OEt2 • RaNi • Hydroxide, sodium • NEtiPr2 • Chloromethyl ether • Hydroxide, sodium • I2 • HSnBu3 • AIBN • LiNiPr2, HMPA • MoOPH • Me2S • BF3·OEt2 • HMPA (solvent) • Perbenzoic acid, 3-chloro • |