Total synthesis of Hirsutene (Krische):
| Reference: | Krische, M. J.; Wang, J.-C. Angew. Chem IE. 2003, 42, 5855. DOI |
| Reactions: | HWE → Enone • CompE+-Aldehyde/CarboxEster+M-R • Li-Alkynyl+Chlorocarbonate • Li-Alkynyl+Alkyl-X • Alkyl-X+Li-R • Aldol-Na → Enone • Cyclopentenone • Bicyclo(330) • Ozonolysis • CompOx-Alkene/Alkyne+O3 • Mechanism • Cycloaddition Allyl anion • Cyclopentene • Bicyclo(330) • Hydrogenation EnoateEster • CarboxEster → Alkyl-OH • Alkyl-OH → Aldehyde • Li/H → Li-Alkynyl • O-H → O-SO2Ar • |
| Reagents: | TsCl, Py • Alkynyl-Li • Me-Li • O=C(OMe)Cl • O3; PPh3 • P(O)(OR)2CHR-C(O)R' • NaH • H2, Pd • AlH4-Li+ • DMSO, (COCl)2 (Swern) • NH3 • DMSO (solvent) • PBu3 • |