Total synthesis of Hinesol:
| Reference: | Chass, D. A.; Buddhasukh, D.; Magnus, P. D. J. Org. Chem. 1978, 43, 1750. DOI |
| Reactions: | Reformatsky • CarboxEster enolate+Ketone • Ether-5 • CarboxEster → CarboxEster-α-SeR • Na/H → Na-Sulfone • Selenoxide-Ei → EnoateEster • CarboxEster → EnoateEster • Cu-Me+EnoateEster • ConjAdd Cu-Me • Ketone+Mg-Alkyl • Mg-Alkyl+Ketone • Li-Sulfone+Alkyl-X • Alkyl-X+Li-R • Epoxide reduction • Wagner-Meerwein • Mechanism • Bicyclo(221) • Alkyl-X → Alkyl-CN • Dehydration → Ene • Epoxidation, peracid • Diol-1,3 → Ketal • Na/H → Na-Sulfone • Grob fragmentation • Mechanism • Li-Sulfone+Ketone • Spiro(54) • Barton remote functionalization • Lactone-5 • Nitrile → CarboxAcid • Diol-1,3 → Ketal • Ketal → Diol-1,3 • O-H → O-SO2Ar • CompNu-O-H/O-H+RSO2X • Alkyl-OH → Ketone • CarboxEster → Alkyl-OH • Fischer esterification • CarboxAcid → CarboxEster • CarboxEster → Alkyl-OH • O-H → O-SO2Ar • Alkyl-SO2R → Alkyl-H • O-C(O)R → O-H • O-H → O-SO2Ar • |
| Reagents: | Bromoacetate • Bromoacetate • Zn° • HgO • AlH4-Li+ • TsCl, Py • Cyanide, sodium • Hydroxide, sodium • HOMe (react) • BF3·OEt2 • LiNiPr2 • Periodate, sodium • Me-Cuprate • H2SO4 • Acetone (react) • AlH4-Li+ • TsCl, Py • NaH • TsCl, Py • CrO3·Py2 (Collins) • Al(Hg) • Me-MgI • Bicarbonate, sodium • AlH4-Li+ • Burgess reagent • Diselenide, phenyl • Acetic anhydride • Photochemistry • DMSO (solvent) • DMSO (solvent) • CuSO4 • NaH • LiCHR-Sulfonyl • LiCHR-Sulfonyl • DMSO (solvent) • Perbenzoic acid, 3-chloro • |