Total synthesis of Paniculatine:
| Reference: | Sha, C.-K.; Lee, F.-K.; Chang, C.-J. J. Am. Chem. Soc 1999, 121, 9875. DOI |
| Reactions: | Si-Aryl → H-Aryl • Alkyl-OH → Ketone • Ketone → Alkyl-OH • O-SiMe2tBu → O-H • ConjAdd-Silylation • Enone+Cu-R • Cu-Alkyl+Enone • ConjAdd Cu-Alkyl • Mg-R → Cu-R • Si-Alkyl → HO-Alkyl • Allylic oxidation → Allyl-OH • ConjAdd EnolSilane • Enone+EnolSilane • Ketene acetal+Enone • Mukaiyama-Michael • Radical cyclization(α-Keto) • Cyclopentene • Bicyclo(430) • Bicyclo(330) • EnolSilane → Ketone-α-Halo • Ketone → Ketone-α-Halo • Ketone → Alkyl-OH • Si-Vinyl → H-Vinyl • Alkyl-OH inversion • O-H → O-Bn • O-H → O-SiMe2tBu • Allyl-OH → Enone • Alkyl-OH → CarboxAcid • CarboxAcid → CarboxCl • CarboxAcid → CarboxAmide • CarboxEster → CarboxAmide • N-C(O)R → N-CH2R • Amine-6 • Bicyclo(430)-aza • Alkyl-OH → Ketone • CompOx-Alkyl-OH/Amine+DMSO • O-Bn → O-H • CompRed-Benzyl-X/Ketone+H2 • CarboxAmide epimerization • |
| Reagents: | Alkyl-MgX • Alkynyl-SiR3 • CuI • Perbenzoic acid, 3-chloro • I2 • Li°/NH3 • Fluoride, R4N+ • H2O2, K2CO3 • Imidazole • CrO3Cl·PyH (PCC) • BH(sBu3)-Li+ • Benzyl-X • Acetic acid, trifluoro • SeO2 • DMSO, (COCl)2 (Swern) • Ketene acetal • LiClO4 • Acetic acid • CrO3, H2SO4 (Jones) • Oxalyl chloride • NH2Me • Carbonate, potassium • AlH4-Li+ • DMSO, (COCl)2 (Swern) • H2, Pd • HSnBu3 • AIBN • KH • |