Total synthesis of Darwinolide New:
| Reference: | Siemon, T.; Steinhauer, S.; Christmann, M. Angew. Chem. Int. Ed. 2019, 58, 1120. DOI |
| Reactions: | MeOH (react) • O-Bn → O-H • O-SiMe2tBu → O-H • O-H → O-C(O)R • Claisen-Ireland • CarboxAcid → Alkyl-OH • Alkyl-OH → Aldehyde • CarboxAnhydride → Alkyl-OH • Alkyl-OH → Aldehyde • Aldehyde → Acetal • Alkene → Diol-1,2 • O-H → O-C(O)R (asym) • Asymmetric desymmetrization • CompNu-O-H/O-H+RC(O)X • Alkyl-OH → Ketone-α-OR • O-C(O)R → O-H • Ketone-α-OH cleavage • Criegee oxidation • Aldehyde → Alkyl-OH • O-H → O-SiMe2tBu • CarboxEster enolate+Aldehyde • Alkyl-OH → Ketone • Alkyl-OH → Alkyl-I • Alkyl-X → Alkyl-SeR • Selenoxide-Ei → Ene • RCM → Ring-C • Cycloheptane • Ketone epimerization • Hydrogenation alkene • Ketone → EnolTriflate • Al-Me+Enone-β-X • ConjAdd-Elimination • Pd/Al-Alkyl+Vinyl-X • Acetal → Acetal • |
| Reagents: | Carbodiimide • DMAP • LiN(SiMe3)2 • SiMe3-Cl • AlH4-Li+ • O2 • CuOTf • AlH4-Li+ • DMSO, (COCl)2 (Swern) • NEtiPr2 • TsOH • OsO4-22K+ • Fe(CN)6K3 • DBU • Benzoyl chloride • Chiral catalyst (diamine) • NEt3 • IBX • Carbonate, potassium • BH4-Na+ • SiMe2tBu-Cl • NaN(SiMe3)2 • Dess-Martin • H2, Pd • HCl, H2O • I2 • H2O2 • H2, Pd • Tf2O • NaN(SiMe3)2 • AlMe3 • Pd2(dba)3 • Acetic acid • Acetic anhydride • H2SO4 • Chiral catalyst (diamine) • Selenocyanate, o-nitrophenyl • BH4-Na+ • |