Total synthesis of Cylindrocyclophane F:
| Reference: | Smith, A. B.; Kozmin, S. A.; Paone, D. V J. Am. Chem. Soc. 1999, 121, 7423-7424. DOI |
| Reactions: | CarboxAmide(Evans) → CarboxEster • O-H → O-MOM • O-Bn → O-H • Li/I → Li-Alkyl • O-MOM → O-H • Li-Dibromomethyl+CarboxEster • CarboxEster+Li-R • Kowalski reaction • Li-Dibromomethyl+CarboxEster • CarboxEster+Li-R • Kowalski reaction • O-MOM → O-H • Danheiser benzannulation • CarboxAmide enolate(Evans)+Alkyl-X • Allyl-X+Enolate (asym) • Li-Alkyl+Ketone • Enone-β-OR+Li-R • Stork-Danheiser • Wittig-methyl • RCM → Ring-C • Paracyclophane • Ynol-OSi • O-H → O-Alkyl (phenol) • Benzene synthesis • Lemieux-Johnson oxidation • Alkyl-OH → Alkyl-I • Hydrogenation alkene • Li/I → Li-Alkyl • Mechanism • Myers reductive coupling • Li-Alkyl+Imine • Hydrazone+Li-R • O-Me → O-H (phenol) • CarboxAcid → CarboxEster • Williamson esterification • CarboxEster → Alkyl-OH • Alkyl-OH → Alkyl-I • Alkyl-OH → Aldehyde • Alkene cleavage • Aldehyde → Hydrazone • Ketene synthesis • Diels-Alder-inverse, EnolEther • Electrocyclic-4π • N-H → N-SiMe2tBu • |
| Reagents: | NaN(SiMe3)2 • H2O2, LiOH • Carbonate, potassium • CH2Br2 • BuLi(n) • CH2Br2 • BuLi(n) • AlH4-Li+ • Chloromethyl ether • H2, Pd • PPh3, I2 • Alkyl-Li • BuLi(tert) • Fluoride, R4N+ • Carbonate, potassium • HCl, H2O • PPh3, I2 • LiCHBr2 • LiCHBr2 • HCl, MeOH • Dess-Martin • PPh3=CH2 • H2, Pd • B(Br)3 • Allyl-Br • Grubbs I • SiiPr3-OTf • Imidazole • BuLi(tert) • LiTMP • LiTMP • OsO4, NaIO4 • Hydrazine, tosyl • SiMe2tBu-OTf • HOEt (react)} • |