Total synthesis of Guanacastepene E:
| Reference: | Miller. A. K.; Hughes, C. C.; Kennedy-Smith, J. J.; Gradl, S. N.; Trauner, D. J. Am. Chem. Soc. 2006, 128, 17057. DOI |
| Reactions: | Mg-R → Ce-R • Ether-5 • O-Bn → O-H • O-H → O-C(O)R • O-MOM → O-H • O-SiMe2tBu → O-H • Pd-Heck coupling • Cyclohexane • Furan synthesis • RCM → Enone • Cyclopentenone • Li/I → Li-Aryl • Li/I → Li-Alkyl • Alkyl-OH → Alkyl-I • Ce-Vinyl+Aldehyde • Aldehyde+Ce-R • Ketone → Alkyl-OH (asym) • Cu-Alkyl+Enone • Enone+Cu-R • ConjAdd Cu-Alkyl • EnolSilane Oxidative coupling • Oxidative coupling enolate • Electrolysis • Cycloheptane • Bicyclo(540) • Bicyclo(530) • Alder ene reaction • Allyl-OH → Enone • O-H → O-Bn • CarboxEster → Aldehyde • Li-Aryl+Aldehyde • Alkyl-OH → Ketone • Hydroboration → Alkyl-OH • O-H → O-SiMe2tBu • Ketone → EnolSilane • Ketone → Alkyl-OH • Ether-5 • Reductive etherification • Ether-5 • Bicyclo(430)-oxa • O-H → O-MOM • Diol-1,2 → Ketone-α-OR • O-C(O)R → O-H • CompE+-CarboxEster/CarboxEster+H2O • |
| Reagents: | Furyl-Li • BuLi(n) • Dess-Martin • B(Cl)(Ipc)2 • Pd(OAc)2 • Bromide, R4N+ • BH-BBN • H2O2, NaOH • PPh3, I2 • SnCl4 • NaH • AlHiBu2 • Vinyl-MgX • CeCl3 • Dess-Martin • Grubbs II • BuLi(tert) • CuCN • KN(SiMe3)2 • 18-crown-6 • SiMe2tBu-OTf • SiMe2tBu-Cl • Electrolysis • LiClO4 • AlHiBu2 • Chloromethyl ether • Na°/NH3 • Acetic anhydride • BF3·OEt2 • Me2S • Fluoride, R4N+ • Dess-Martin • Carbonate, potassium • Alkyl-Li • Furyl-Li • Chiral auxiliary (boronate) • HOMe (react) • Imidazole • Chiral auxiliary (alcohol) • Chiral auxiliary (alcohol) • Benzyl-X • |