title: Asymmetric, stereodivergent synthesis of (-)-clusianone utilizing a biomimetic cationic cyclization.
abstract: We report a stereodivergent, asymmetric total synthesis of (-)-clusianone in six steps from commercial materials. We implement a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms. Mechanistic studies point to the unique ability of formic acid to mediate the cyclization forming the clusianone framework.
authors.affiliation: Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA).
authors.forename: Jonathan H
authors.initials: JH
authors.lastname: Boyce
authors.forename: John A
authors.initials: JA
authors.lastname: Porco
mesh_terms: D001577:Benzophenones / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D016227:Benzoquinones / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D001688:Biological Products; D032701:Biomimetics; D002412:Cations; D003500:Cyclization; D005561:Formates / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: C118110:7-epiclusianone; D001577:Benzophenones; D016227:Benzoquinones; D001688:Biological Products; D002412:Cations; D005561:Formates; C030544:formic acid
keywords: PPAPs; cationic cyclization; dearomatization; formic acid; natural products