Total synthesis of Quadrone (Danishefsky):
| Reference: | Danishefsky, S.; Vaughan, K.; Gadwood, R. C.; Tsuzuki, K. J. Am. Chem. Soc. 1981, 103, 4136. DOI |
| Reactions: | O-H → O-SO2Me • Finkelstein reaction • Alkyl-X → Alkyl-Br • Ketal → Ketone • Ketal → Ketone • Ketone → Ketone-α-SeR • Selenoxide-Ei → Enone • Ketone → Enone • Ketene acetal+β-DicarbonylEnone • Enone+EnolSilane • ConjAdd EnolSilane • Mukaiyama-Michael • Aldol-Li → Aldol • Enone enolate+Aldehyde • Hydrogenation Enone • Hydroboration → Alkyl-OH • CompRed-Alkene/Ketone+M-H • Aldol-Na → KetoEsterEnone • Knoevenagel condensation • Cyclopentenone • Bicyclo(330) • Lactone-6 • ConjAdd-Alkylation • Cu-Vinyl+Enone • Ketone enolate+Alkyl-X • Bromoacetate+Enolate • Mg-R → Cu-R • CarboxEster enolate+Alkyl-X • Cyclohexane • Alkyl-X+Enolate (intram) • Bicyclo(430) • Alkyl-OH → Alkyl-Br • Ketone → Ketal • Alkyl-X → Alkyl-I • Finkelstein reaction • CarboxAcid → CarboxEster • Decarboxylation β-keto acid • CarboxEster → CarboxAcid • CarboxEster → CarboxAcid • Ketone → Ketal • |
| Reagents: | Glycol • TsOH • BH3 • Sulfonyl chloride, methane • Bromide, lithium • NaOMe • Ketene acetal • TiCl4 • HCl, H2O • Diazomethane • Glycol • Iodide, sodium • LiN(SiMe3)2 • Hydroxide, potassium • SePh-Cl • H2O2 • LiNiPr2 • Formaldehyde • H2, Pt • H2O2, NaOH • HMPA (solvent) • Vinyl-MgX • CuI·PBu3 • Allyl-Br • |