title: Reagent control of [1,2]-Wagner-Meerwein shift chemoselectivity following the Nazarov cyclization: application to the total synthesis of enokipodin B.
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.
authors: Department of Chemistry, University of Rochester, Rochester, NY 14627, USA.
authors: David
authors: D
authors: Lebœuf
authors: Christopher M
authors: CM
authors: Wright
authors: Alison J
authors: AJ
authors: Frontier
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003500:Cyclization; D007202:Indicators and Reagents; D008024:Ligands; D015394:Molecular Structure; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D013237:Stereoisomerism
chemical_list: D007202:Indicators and Reagents; D008024:Ligands; D012717:Sesquiterpenes; C539534:enokipodin B; D003300:Copper