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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
Keywords: Jones oxidation • Alkyl-OH → Ketone • Sulfide-5 • O-H → O-MEM • Sulfide → Sulfoxide • O-H → O-SO2R • Dehydration → EneSulfide • Sulfoxide → Sulfide • O-H → O-SiMe2tBu • Li/H → Li-Vinyl-OR • Allyl-OH → Enone • Spiroketal • Ether-5 • CompRed-Ketone/Ketone+B-H • O-H → O-SiMe2tBu • Alkene isomerization • O-Allyl → O-H • O-SiMe2tBu → O-H • Li/H → Li-Vinyl-OR • Hydroboration EneSulfide • CompRed-EneSulfide/CarboxEster+B-H • Epoxidation, Mo • Selenoxide-Ei → Enone • Ketone → Enone • CarboxEster → Aldehyde • Epoxide → Allyl-OH • Li-Vinyl+Aldehyde • Felkin-Anh • Ozonolysis • Ketone → EnolEther • ConjAdd M-OR • Ketone → Ketone-α-Halo • Ketone → Ketone-α-OR • Ketone enolate+(Ox) • Ketone → Alkyl-OH •
Reagents: LiNiPr2 • Se(O)Ph-Cl • Hydroperoxide, tbutyl • CrO3, H2SO4 (Jones) • KH • O3 • Me2S • Epoxide • DBU • LiNiPr2 • NCS • Thiol, acetyl • NaOMe • DMAP • Oxaziridine • Sulfonyl chloride, methane, NEt3 • DBU • Acetic anhydride, trifluoro • AlHiBu2 • BH3 • H2O2, NaOH • Vinyl-Li • BuLi(tert), HMPA • Oxalic acid • DMSO, (COCl)2 (Swern) • TsOH • BH(sBu3)-Li+ • SiMe2tBu-OTf • Carbonate, cesium • KN(SiMe3)2 • Oxaziridine, Camphor • Rh(PPh3)3Cl • HCl, MeOH • H2O2, Mo • Sulfate, dimethyl • 18-cr-6 • BH4-Na+ • Mo(CO)6

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