Total synthesis of Steenkrotin A:
| Reference: | Ding, H. et al Angew. Chem. Int. Ed. 2015, 54, 6905. DOI |
| Reactions: | Ketone → EnolSilane • Ketone → EnolSilane • O-SiMe2tBu → O-H • O-H → O-C(O)R • Rubottom oxidation • Ketone → Ketone-α-OR • EnolSilane+peracid • Li-Allyl+Ketone • Ketone+Li-Alkyl • Carbene Cycloaddition • Cyclopropane • Bicyclo(510) • O-H → O-Alkyl • CarboxEster enolate+Alkyl-X • Alkyl-X+Enolate • Alkyl-OH → Aldehyde • Prins • Ether-5 • Bicyclo(530)-oxa • Radical cyclization(Alkyl) • Sm-Alkyl+Aldehyde • Aldehyde+Sm-R • Cyclopentane • Spiro(64) • Retro-Aldol • O-C(O)R → O-H • Aldol-K → Aldol • Aldol-K → Aldol • ConjAdd M-OR • Cyclohexane • Bicyclo(321)-oxa • Mechanism • Dehydroalkoxylation → Enone • Retro-Aldol • Ketone epimerization • O-H → O-Ethoxyethyl • Alkyl-OH → Ketone • Alkyl-OH → Aldehyde • CarboxEster → Alkyl-OH • Allyl-OH → Enone (rearr) • O-H → O-C(O)R • CompNu-O-H/O-H+RC(O)X • |
| Reagents: | SiMe2tBu-OTf • Perbenzoic acid, 3-chloro • Allyl-Li • CrO3Cl·PyH (PCC) • SiMe3-OTf • BuLi(n) • MeI • AlH4-Li+ • Acetic anhydride, NEt3 • Dess-Martin • HF·Py • SmI2 • HMPA (solvent) • SmI2 • Dess-Martin • Carbonate, potassium • HOMe (react) • Hydroxide, lithium • Diazomalonate • |