Total synthesis of Ingenol:
| Reference: | Jorgensen, L.; McKerral, S. J.; Kuttruff, C. A,; Ungeheuer, F.; Felding, J.; Baran, P. S. Science, 2013, 341, 878 DOI |
| Reactions: | O-H → O-SiMe3 • O-SiMe2tBu → O-H • Ketone+Mg-Alkynyl • Pauson-Khand • Cycloheptane • Cyclopentenone • Bicyclo(530) • Bicyclo(540) • Mg-Alkyl+Ketone • Alkene → Diol-1,2 • CompOx-Alkene/Alkene+OsO4 • Diol-1,2 → Carbonate • Pinacol • Cycloheptane • Bicyclo(441) • Allylic oxidation → Allyl-OH • Dehydration → Ene • Allylic oxidation → Allyl-OH • O-H → O-C(O)R • Allylic oxidation → Allyl-Cl • Ozonolysis • Aldehyde+Ketone enolate • Bicyclo(410) • O-H → O-SiMe2tBu • Ketone enolate+Me-I • |
| Reagents: | NCS • LiN(SiMe3)2 • Alkynyl-MgX • Rh(CO)2Cl • Me-MgBr • SiMe3-OTf • OsO4 • BF3·OEt2 • SeO2 • Martin sulfurane • HF • SeO2 • O3 • Acetic anhydride • Hydroxide, sodium • SiMe2tBu-OTf • MeI • CO • HMPA (solvent) • Formic acid • |