Total synthesis of Breynolide:
| Reference: | Smith, A. B. III; Empfield, J. R.; Rivero, R. A.; Vaccaro, H. A.J. Am. Chem. Soc., 1991, 113, 4037. DOI J. Am. Chem. Soc., 1992, 114, 9419-9434. |
| Reactions: | Sulfide-5 • O-H → O-SO2Me • Li/H → Li-Vinyl-OR • O-SiMe2tBu → O-H • Li/H → Li-Vinyl-OR • EneSulfide hydroboration • Hydroboration → Alkyl-OH • CompRed-EneSulfide/CarboxEster+M-H • Epoxidation, Mo • Selenoxide-Ei → Enone • Ketone → Enone • CarboxEster → Aldehyde • Epoxide → Allyl-OH • Li-Vinyl+Aldehyde • Felkin-Anh • Ozonolysis • Ketone → EnolEther • ConjAdd M-OR • Enone+O-R • Ketone → Ketone-α-Halo • Ketone enolate+Cl2 • Ketone → Ketone-α-OR • Oxaziridine+Enolate • Alkyl-X → Alkyl-SR • Sulfide → Sulfoxide • Alkene isomerization • Pd-Deallylation • Jones oxidation • Alkyl-OH → Ketone • O-H → O-MEM • Ketone → Alkyl-OH • O-H → O-SiPh2tBu • Ketal → Ketone • Sulfoxide → Sulfide • Dehydration → EneSulfide • O-Allyl → O-H • Allyl-OH → Enone • CompOx-Alkyl-OH/Sulfide+DMSO • Spiroketal • Ether-5 • Ketone → Alkyl-OH • CompRed-Ketone/Ketone+M-H • O-H → O-SiMe2tBu • ConjAdd M-SR • Enone+Thiolate • Sulfide-5 • Bicyclo(430)-thia • |
| Reagents: | LiNiPr2, HMPA • Se(O)Ph-Cl • Hydroperoxide, tbutyl - Mo • CrO3, H2SO4 (Jones) • KH • O3 • Me2S • Epoxide • DBU • LiNiPr2 • NCS • Thiol, acetyl • NaOMe • Oxaziridine • Sulfonyl chloride, methane, NEt3 • DBU • Acetic anhydride, trifluoro • SiPh2tBu-OTf • AlHiBu2 • BH3 • H2O2, NaOH • Vinyl-Li • BuLi(tert), HMPA • Oxalic acid • DMSO, (COCl)2 (Swern) • TsOH • BH(sBu3)-Li+ • SiMe2tBu-OTf • HO-Allyl • Carbonate, cesium • KN(SiMe3)2 • Oxaziridine, Camphor • Rh(PPh3)3Cl • HCl, MeOH • H2O2, Mo • Sulfate, dimethyl • 18-crown-6 • HOMe (react) • BH4-Na+ • HMPA (solvent) • MEM-Cl • DMAP • |