Total synthesis of Crotogoudin:
| Reference: | Breitler, S.; Carreira, E. M. Angew. Chem. Int. Ed. 2013, 52, 11168–11171. DOI |
| Reactions: | O-Bn → O-H • Iodonium • O-SiMe2tBu → O-H • Michael Enal • Robinson annulation, ketoester • Aldol-Base → Enone • Cyclohexenone • Decarboxylation Krapcho • ConjReduct Enone • Aldol-Acid → Aldol • Bicyclo(222) • Cyclohexanone • Cyclopropane • Radical cyclization(Ketyl) • Reductive elimination - X/OR • Lactone-6 • Bicyclo(440) • Decarboxylation Krapcho • Mannich • Iminium+Enolate • Mg-Vinyl+Ketone • Ketone+Mg-Vinyl • Hofmann elim → Enone • Ketone → Alkyl-OH (asym) • Allylic oxidation → Allyl-OH • O-H → O-C(O)R • O-H → O-SiMe2tBu • CompNu-O-H/O-H+R3Si-X • Lactone-5 • Alkyl-OH → Ketone • Lactone → Ketene acetal • Alkyl-OH → Aldehyde • Alkyl-OH → Ketone • Amine → Ammonium • |
| Reagents: | Acetoacetate • Crotonaldehyde • DBU • Chloride, lithium • Na°/NH3 • DMSO, (COCl)2 (Swern) • HCl • Dess-Martin • Baker's yeast • Propenyl-MgX • LaCl3 • SiMe2tBu-OTf • Lutidine • Iodonium ylide • Rh2(esp)2 • Bicarbonate, sodium • SeO2 • Hydroperoxide, tbutyl • BH4-Na+ • DMAP • SmI2 • DMPU (solvent) • Chloride, lithium • Dess-Martin • SiiPr3-OTf • NEt3 • LiN(SiMe3)2 • MeI • Al2O3 • CH2=NMe2+I- • |