Total synthesis of Rubriflordilactone B:
| Reference: | Yang, P.; Yao, M.; Li, J.; Li, Y.; Li, A. Angew. Chem. Int. Ed. 2016, 55, 6964. DOI |
| Reactions: | Luche reduction • Enone → Allyl-OH • O-SiMe2tBu → O-H • Lactone → Lactol • CompRed-Enone/Enone+M-H • Nitrile → CarboxAcid • Lactone-5 • O-H → O-SiEt3 • Alkyl-X → Alkyl-SeR • Arbuzov • Alkyl-X → Alkyl-PRn • Ozonolysis • CompOx-Alkene/Alkene+O3 • HWE → Enone (intram) • Cycloheptane • Sulfimide-Ei → Enone • Ketone → Enone • Enone enolate+Sulfinyl-Cl • ConjReduct Enone • Enone → Ketone • ConjAdd M-CN • Alkene → Alkyl-OH • CarboxEster → CarboxEster-α-OR • Oxaziridine+Enolate • Ketone → EnolTriflate • O-H → O-C(O)R • Dieckmann • CarboxEster enolate+CarboxEster • Lactone-5 • Allylic oxidation → Allyl-Br • Wohl-Ziegler bromination • Selenoxide-Ei → Diene • Enone → Enone-α-Halo • Pd/H-Alkynyl+Vinyl-X • Electrocyclic-6π • Benzene synthesis • Dehydrogenation • Pd/H-Alkynyl+Vinyl-X • Claisen-Johnson • CarboxEster epimerization • HWE → EnoateEster • Wittig-methyl • CompE+-Ketone/CarboxEster+Wittig • Alkyne → Ene-cis (Lindlar) • CompRed-Alkyne/Alkene+H2 • ConjAdd M-OR • Ether-5 • Bicyclo(330)-oxa • Ozonolysis • Ketone → Alkyl-OH • Reductive etherification • Bicyclo(530)-oxa • O-SiEt3 → O-H • Lactone-5 • |
| Reagents: | BH4-Na+, CeCl3 • Alkynyl-SiR3 • Fluoride, R4N+ • AlHiBu2 • DBU • P(O)(OR)2CH2-Vinyl • ZnI2 • P(OEt)3 • O3; Me2S • P(O)(OR)2CH2-C(O)R' • Carbonate, potassium • LiNiPr2 • Imidazole • BH(sBu3)-Li+ • Cyanide, trimethylsilyl • AlEt3 • HSiPhH2 • Hydroxide, sodium • PPh3=CH2 • KN(SiMe3)2 • Oxaziridine • SiEt3-OTf • O3 • LiN(SiMe3)2 • Tf2NPh • Sc(OTf)3 • Acetic anhydride • LiN(SiMe3)2 • BF3·OEt2 • NBS • Benzoyl peroxide • Selenolate, phenyl • BH4-Na+ • H2O2 • LiTMP • Pd(PPh3)4 • CuI • NEtiPr2 • H2, Pd • DDQ • |