title: A Unified Approach for the Enantioselective Synthesis of the Brominated Chamigrene Sesquiterpenes.
abstract: The brominated chamigrene sesquiterpenes constitute a large subclass of bromocyclohexane-containing natural products, yet no general enantioselective strategy for the synthesis of these small molecules exists. Herein we report a general strategy for accessing this family of secondary metabolites, including the enantioselective synthesis of (-)-α- and (-)-ent-β-bromochamigrene, (-)-dactylone, and (+)-aplydactone. Access to these molecules is enabled by a stereospecific bromopolyene cyclization initiated by the solvolysis of an enantiomerically enriched vicinal bromochloride.
authors: Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA, 94305, USA.
authors: Alexander J
authors: AJ
authors: Burckle
authors: Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA, 94305, USA.
authors: Vasil H
authors: VH
authors: Vasilev
authors: Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA, 94305, USA. nburns@stanford.edu.
authors: Noah Z
authors: 0000-0003-1064-4507
authors: NZ
authors: Burns
mesh_terms: D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D061565:Cycloaddition Reaction; D054879:Halogenation; D008968:Molecular Conformation; D012717:Sesquiterpenes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001688:Biological Products; D012717:Sesquiterpenes; C000626806:chamigrene
keywords: asymmetric synthesis; halogenation; natural products; solvolysis; terpenes