Total synthesis of Himalensine A:
| Reference: | Shi, H.; Michaelides, I. N.; Darses, B.; Jakubec, P.; Nguyen, Q. N. N.; Paton, R. S.; Dixon, D. J. J. Am. Chem. Soc. 2017, 139, 17755-17758. DOI |
| Reactions: | ConjAdd-Aldol • Grob fragmentation • Decarboxylation β-keto acid • Ketone → Ketal • CarboxAcid → CarboxF • CarboxF → CarboxAmide • Ketal → Ketone • Alkene isomerization • Diels-Alder, Intram, Ene (asym) • Furan cycloaddition • Bicyclo(221)-oxa • Lactam-5 • Bicyclo(540) • Bicyclo(530)-aza • Hydrogenation Enamine • CompRed-Enol/Enamide+H2 • N-H → N-Propargyl • Ketone → Alkyl-OH • Dehydrosulfonoxylation → Enone • Enone → EnolSilane • Radical cyclization(Vinyl) • Amine-6 • Sn-Vinyl → H-Vinyl • Hydrogenation Alkene • EnolSilane → Ketone-α-Halo • Dehydrohalogenation → Enone • Ketone-α-Halo → Enone • Allylic oxidation → Enone • Enone → EnolTriflate • Pd/Zn-Alkyl+Vinyl-X • Acetal → Aldehyde • Stetter • Cyclopentanone • Bicyclo(530) • CarboxAmide → Hemiaminal • N-C(O)R → N-CH2R • Leuckhart • Alkene isomerization • |
| Reagents: | Propiolate • HCl • NaH • DMSO (solvent) • Glycol, bistrimethylsilylether • SiMe3-OTf • Hydroxide, potassium • Cyanuric fluoride • NaN(SiMe3)2 • TsOH • Acetic acid, trifluoro • H2, Pd • Propargyl-Br • NaN(SiMe3)2 • AlH4-Li+ • Sulfonyl chloride, methane, NEt3 • SiiPr3-OTf • HSnBu3 • AIBN • Sulfonic acid, Camphor • Crabtree catalyst • H2, Ir • NBS • TsOH·Py • O2 • NaN(SiMe3)2 • Tf2NPh • HCl, H2O • Thiazolium • NEt3 • H2, Ir • Vaska's catalyst • Formic acid • HSiMe2-O-SiMe2H • Ir(cod)X • |