Total synthesis of Deacetoxyalcyonin Acetate:
| Reference: | MacMillan, D. W. C.; Overman, L. E. J. Am. Chem. Soc. 1995, 117, 10391. DOI |
| Reactions: | Enone → EnolTriflate • CarboxEster → Alkyl-OH • O-SiiPr3 → O-H • O-SiMe2tBu → O-H • Si-Alkynyl → H-Alkynyl • Li-Alkynyl+Epoxide • Epoxide+Li-R • Li/H → Li-Alkynyl • Wittig-methoxymethyl • Reductive formylation • Nozaki-Hiyama coupling • Cr-Vinyl+Aldehyde • Aldehyde+Cr-R • Cyclodecane • Sharpless epoxidation • Sn-Vinyl → I-Vinyl • Pd-Stannylation • Epoxide reduction • Haloboration Alkyne • Alkyne → Vinyl-I • Photochemistry • Prins-Pinacol • Ether-5 • Bicyclo(420)-oxa • Mechanism • Alkyl-OH → Aldehyde-α-OR • O-H → O-Piv • O-H → O-SiMe2tBu • Alkyl-OH → Aldehyde • Decarbonylation • C-C(O)H → C-H • B-Vinyl → H-Vinyl • Li/I → Li-Vinyl • O-Piv → O-H • O-H → O-Methoxypropyl • Aldehyde+Li-Vinyl • O-Methoxypropyl → O-H • EnolEther → Aldehyde • O-H → O-C(O)R • |
| Reagents: | Acetic acid • LiNiPr2 • SnMe3-SnMe3 • Vinyl-Li • BuLi(tert) • Epoxide • Alkynyl-Li • BF3·OEt2 • Propenyl-OR • AlHiBu2 • RuO4-Pr4N+, NMO • AlH2(OR)2-Na+ • Piv-Cl • SiMe2tBu-OTf • AlHiBu2 • RuO4-Pr4N+, NMO • PPh3=CH-OR • TfOH • NiCl2 • CrCl2 • DMSO (solvent) • Acetic anhydride, Py • Fluoride, R4N+ • Tf2NPh • Photochemistry • Pd(PPh3)4 • BF3·OEt2 • Vinyl-Li • B(I)BBN • |