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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
Keywords: O-H → O-Me • Ketone → EnolSilane • Ketone → Ketone-α-SeR • Ketone → EnolSilane • EnolSilane → Ketone-α-Halo • Hydroboration alkene • O-H → O-SiMe2tBu • Alkyl-OH → Ketone-α-OR • O-SiMe2tBu → O-H • Alkyl-OH → Aldehyde • Aldehyde → CarboxAcid • Ketal → Ketone • Lactone-6 • O-H → O-MOM • Ketone → EnolSilane • Saegusa oxidation • Ketone → Enone • Enone → Ketal(thio) • 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-R • Cu-Vinyl+Enone • Ketone → Ketone-α-Halo • Ketone → Alkene • Shapiro reaction • Epoxidation, peracid • Ketal(thio) → CH2 • Ketone → CH2 • Iodolactonization • Lactone-6 • Alkyl-X → Alkyl-H • Radical reduction(C-I) • Lactone → Lactone-α-OH • Ether-5 •
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 • DMAP • CrO3·Py2 (Collins) • Perbenzoic acid, 3-chloro • 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 • MoOPH • Me2S • BF3·OEt2

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