Total synthesis of Maoecrystal V (Danishefsky) New:
| Reference: | Peng, F.; Danishefsky, S. J. J. Am. Chem. Soc. 2012, 134, 18860-18867. DOI |
| Reactions: | O-C(O)R → O-H • ConjAdd-Elimination • ConjAdd Enolate • EnoateEster enolate+Enone • CarboxEster → Alkyl-OH • Enone → Allyl-OH • Allyl-OH → Enone • O-H → O-C(O)R • Enone → EnolSilane • Diels-Alder, Intram, Ene • Lactone-6 • Bicyclo(222) • Spiro(55)-oxa • EnolSilane → Ketone • Dehydrosulfonoxylation → EnoateEster • EnoateEster epoxidation, nucleophilic • Epoxide → Iodohydrin • Alkyl-X → Alkyl-H(2°) • Radical reduction(C-I) • Epoxidation, peracid • Epoxide → Tetrahydrofuran • Ether-5 • O-H → O-C(O)R • Ketone → Alkyl-OH • O-H → O-MOM • O-C(O)R → O-H • Epoxidation, peracid • Diol-1,2 → Ketone-α-OR • Epoxide → Allyl-OH • Dehydroalkoxylation → Enone • O-H → O-C(O)R • ConjAdd M-SR • Enone+Thiolate • Ketone → Alkyl-OH • Alkyl-SR → Alkyl-H • O-H → O-SO2R • Dehydrosulfonoxylation → EnolEther • Epoxidation, dioxirane • Pinacol • Pinacol • Takai-Lombardo → Ene • Ketone → C=CH2 • Simmons-Smith • Cyclopropane • Alkyl-OH → Ketone • Hydrogenolysis Cyclopropane • Takai-Lombardo → Ene • Ketone → C=CH2 • Alkene isomerization • Ketone → EnolSilane • Saegusa oxidation • Ketone → Enone • Epoxidation, dioxirane • |
| Reagents: | LiNiPr2 • AlHiBu2 • MnO2 • Fluoride, R4N+ • SiMe2tBu-OTf • NEt3 • Butadiene, 2-OR • H2O2, NaOH • MgI2 • HSnBu3 • AIBN • Perbenzoic acid, 3-chloro • TsOH • Acetic anhydride, Py • BH4-Na+ • Chloromethyl ether • NEtiPr2 • Carbonate, potassium • Perbenzoic acid, 3-chloro • Dess-Martin • Thiol, phenyl • BH4-Na+ • Acetic anhydride, NEt3 • Sulfonyl chloride, methane • DMAP • Dioxirane • Carbonate, potassium • BF3·OEt2 • CH2I2, Zn/Ag • CH2Br2, Zn°, TiCl4 • CrO3Cl·PyH (PCC) • H2, Pt • CH2Br2, Zn°, TiCl4 • TsOH • LiNiPr2 • SiMe3-Cl • Pd(OTFA)2 • Dioxirane • BF3·OEt2 • |