Total synthesis of Dendrobine (Carreira):
| Reference: | Kreis, L. M.; Carreira, E. M. Angew. Chem. Int. Ed. 2012, 51, 3436 –3439. DOI |
| Reactions: | Lactone-5 • Claisen-Ireland • CarboxAcid → CarboxEster • O-SiMe2tBu → O-H • O-SiPh2tBu → O-H • Alkyl-OH → Ketone • Alkyl-OH → Aldehyde • Hydrogenation Enamine • ConjAdd EnAmine • Enone+EnAmine • Cyclopentane • Bicyclo(430) • Ketone → Ketone-α-Halo • Ketone → Ketone-α-NR2 • Bicyclo(330)-aza • Ketone → Alkyl-OH • CarboxEster+Mg-R • Lactone-6 • Alkyl-OH → CarboxAcid • Lactone → Ketene acetal • Mechanism • CarboxEster → Alkyl-OH • O-H → O-C(O)R • Ketal → Diol-1,2 • O-H → O-SiMe2tBu • O-SiMe2tBu → O-H • CompE+-Si-O/Si-O+H2O • Alkyl-OH → Aldehyde-α-OR • Aldehyde+Li-Vinyl • |
| Reagents: | AlH4-Li+ • Benzoyl chloride • NEt3 • DMAP • Acetic acid • SiMe2tBu-Cl • HF·Py • DMSO, (COCl)2 (Swern) • NEt3 • Vinyl-Li • Alkyl-MgBr • TEMPO • Iodosobenzene-OAc • LiNiPr2 • SiMe3-Cl • Diazomethane, silyl • HF·Py • CrO3Cl·PyH (PCC) • H2, Pd • Tribromide • DMAP • BH4-Na+ • DMAP • |