Total synthesis of Eucannabinolide New:
| Reference: | Still, W. C.; Murata, S.; Revial, G.; Yoshihara, K. J. Am. Chem. Soc. 1983, 105, 625-627. DOI |
| Reactions: | Jones oxidation • Allyl-OH → Enone (rearr) • Cycloaddition Ketene • Cyclobutane • ConjAdd M-OR • EnolEther → Ketal • Li-SnR3+Ketone • Li-R → Mg-R • O-H → O-SO2Me • Dehydrosulfonoxylation → Ene • Li/Sn → Li-Vinyl • Enone → Allyl-OH • Epoxidation, peracid • CompOx-Alkene/Alkene+Peracid • Henbest • O-H → O-BOM • Selenolate+Epoxide • Epoxide+M-SeR • Selenoxide-Ei → Allyl-OR • Li-Vinyl+Ketone • Enone+Li-R • Cope rearrangement • Ketal → Ketone • Ketone epimerization • Baeyer-Villiger • Lactone-5 • Enone → Allyl-OH • Lactone → Lactone • Alkyl-OH → Ketone • Ketone epimerization • Ketone → Alkyl-OH • O-BOM → O-H • O-H → O-SiMe3 • Aldol-Li → Aldol • Lactone enolate+Aldehyde • O-H → O-SO2Me • Dehydrosulfonylation → EneLactone • O-SiMe3 → O-H • O-H → O-C(O)R • CompNu-O-H/O-H+RC(O)X • O-H → O-C(O)R • Ketal → Diol-1,4 • |
| Reagents: | Carvone • AlH4-Li+ • Perbenzoic acid, 3-chloro • Chloromethyl ether • Selenolate, phenyl • H2O2 • Bicarbonate, sodium • CrO3, H2SO4 (Jones) • NaOMe • HOMe (react) • SnR3-Li • MgCl2 • Sulfonyl chloride, methane • Carbonate, potassium • DMSO (solvent) • BuLi(n) • KN(SiMe3)2 • Carbonate, potassium • Oxalic acid • H2O2 • Ti(OiPr)4 • NEtiPr2 • NEtiPr2 • BH4-Na+ • Carbonate, potassium • CrO3·Py2 (Collins) • DBU • BH4-Na+ • H2, Pd • SiMe3-Im • Pyridine • LiNiPr2 • Formaldehyde • Sulfonyl chloride, methane, NEt3 • DMAP • DBU • Fluoride, R4N+ • Acetic acid • Carbodiimide • Carbodiimide • DMAP • TsOH·Py • Glycol • |