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Total synthesis of Guanacastepene N:
Reference: Iimura, S.; Overman, L. E.; Paulini, R.; Zakarian, A.; J. Am. Chem. Soc. 2006, 128, 13095. DOI
Keywords: Enone → EnolSilane • Epoxidation, peracid • CompOx-Alkene/Enone+Peracid • Luche reduction • Enone → Allyl-OH • Alkyl-OH → Ketone • O-SiMe2tBu → O-H • Allyl-OH → Enone • Ketone → EnolSilane • O-H → O-C(O)R • O-Bn → O-H • Li/I → Li-Alkyl • Enone enolate+Alkyl-X(2°) • Alkyl-X+Enolate • Mannich • EnolSilane+Iminium • Iminium+Enolate • Claisen acylation, Mander • Ketone enolate+Mander • Allylic oxidation → Allyl-Br • Wohl-Ziegler bromination • Allyl-X → Allyl-OH • Radical oxygenation • Stork-Danheiser • Li-Me+Ketone • Enone-β-OR+Li-R • Hofmann elim → EneLactone • Epoxide reduction • Ketone → EnolTriflate • Cu-Alkyl+Enone • Enone+Cu-R • ConjAdd Cu-R • Ketone → Ketone-α-OR • EnolSilane+Dioxirane • O-H → O-SiMe2tBu • ConjAdd M-OR • Lactone-5 • Pd-Heck coupling •
Reagents: Menthol • TsOH • LiNiPr2 • DMPU (solvent) • MeLi • Bisulfate, sodium • Alkyl-Li • BuLi(tert) • SiMe3-Br • MeI • Carbonate, potassium • Perbenzoic acid, 3-chloro • BH4-Na+, CeCl3 • SiMe2tBu-Cl • Epoxide • BH(Et)3-Li+ • RuO4-Pr4N+, NMO • KN(SiMe3)2 • O=C(OR)CN • Tf2O • HF • RuO4-Pr4N+, NMO • SiEt3-OTf • Dioxirane • Acetic anhydride, NEt3 • HSiEt3, Pd • NBS • Benzoyl peroxide • HSnBu3 • PPh3 • ZnEt2 • CuCN • CH2=NMe2+I- • Imidazole • Pd2(dba)3 • Chiral auxiliary-Menthol •

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