Total synthesis of Cantharidin (Stork):
| Reference: | Stork, G.; van Tamelen, E. E.; Friedman, L. J.; Burgstahler, A. W. J. Am. Chem. Soc. 1951, 73, 4501. DOI Stork, G.; van Tamelen, E. E.; Friedman, L. J.; Burgstahler, A. W. J. Am. Chem. Soc. 1953, 75, 384–392. DOI |
| Reactions: | O-H → O-SO2Me • Diels-Alder, Yne • Furan cycloaddition • Diels-Alder, EnoateEster • Alkene → Diol-1,2 • Alkyl-SR → Alkyl-H • Diol-1,2 cleavage • Li-Aryl+Aldehyde • Ester Pyrolysis • Dehydration → Diene • Ozonolysis • Hydrogenation Alkene • Aldol-enamine → Enal • Cyclopentene • Bicyclo(221) • CarboxEster → Alkyl-OH • Alkyl-X → Alkyl-SR • |
| Reagents: | Acetylene dicarboxylate • AlH4-Li+ • Sulfonyl chloride, methane, Py • Thiolate, ethyl • OsO4 • RaNi • Periodic acid • PhLi • O3 • H2O2 • Butadiene • H2, Pd • |