Reagent Control of [1,2]‐Wagner–Meerwein Shift Chemoselectivity Following the Nazarov Cyclization: Application to the Total Synthesis of Enokipodin B |
| |
Authors: | Dr. David Lebœuf Christopher M. Wright Prof. Alison J. Frontier |
| |
Affiliation: | Department of Chemistry, University of Rochester, Rochester, NY 14627 (USA) |
| |
Abstract: | An approach toward the carbon framework of various sesquiterpenes from the herbertane and cuparane families is described, including the concise total synthesis of enokipodin B. The key step is the construction of the vicinal quarternary centers of the skeleton through a tandem Nazarov cyclization/Wagner–Meerwein rearrangement mediated by a copper(II) complex. During this study, it was also found that changing the ligand architecture on the copper(II) promoter improved the chemoselectivity of the cationic rearrangement. |
| |
Keywords: | copper cyclization rearrangement sesquiterpenes total synthesis |
|