Total synthesis of Limonin (Part 1) New:
| Reference: | Yamashita, S.; Naruko, A.; Nakazawa, Y.; Zhao, L.; Hayashi, Y.; Hirama M. Angew. Chem. Int. Ed. 2015, 54, 8538-8541. DOI (Part 2) |
| Reactions: | Allyl-OH → Allyl-Cl • Epoxidation, peracid • CompOx-Alkene/Alkene+Peracid • Li-Allenyl/Propargyl+Alkyl-X • Alkyl-X+Li-R • CompE+-Alkyl-X/Epoxide+MR • Epoxide → Allyl-OH • Allyl-OH → Allyl-Cl • Allyl-X+Enolate • Ketone enolate+Alkyl-X • Si-Alkynyl → H-Alkynyl • Radical cyclization(α-Keto) • Cyclohexanone • Cyclopentane • Bicyclo(440) • Bicyclo(430) • Ketone-α-Halo → Ketone • Robinson annulation, ketoester • KetoEster enolate+Enone • Cyclohexenone • Bicyclo(440) • Enone enolate+Alkyl-X • Deconjugative alkylation • Alkyl-X+Enolate • Ketone → Alkyl-OH • Aldehyde → Alkyl-OH • O-H → O-SiMe2tBu • CompNu-O-H/O-H+R3Si-X • O-H → O-C(O)R • Epoxidation, peracid • CompOx-Alkene/Alkene+Peracid • Epoxide+M-CN • Cyanide+Epoxide • Retro-Aldol • Mechanism • Allylic oxidation → Enone • ConjReduct Enone • Alkyl-OH → Ketone • O-SiMe2tBu → O-H • Ketone → Alkyl-OH • CompRed-Ketone/Ketone+M-H • O-H → O-SiEt3 • |
| Reagents: | DMF (solvent) • Perbenzoic acid, 3-chloro • Acetoacetate • Allenyl-Li • Al(OiPr)3 • SOCl2 • Mn(OAc)3 • NaH • BuLi(n) • DMPU (solvent) • Zn° • Methyl vinyl ketone • KOtBu • MeI • KOtBu • Carbonate, potassium • Fluoride, R4N+ • AlH4-Li+ • SiMe2tBu-Cl • NaH • Acetic anhydride, Py • DMAP • Perbenzoic acid, 3-chloro • Bicarbonate, sodium • Cyanide, sodium • DMSO (solvent) • Acetic anhydride, Py • Hydroperoxide, tbutyl • Li°/NH3 • Dess-Martin • Fluoride, R4N+ • AlH(OtBu)3-Li+ • SiEt3-OTf • Lutidine • Bicarbonate, sodium • Vilsmeier reagent • |