title: Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes.
abstract: Enantioenriched, polycyclic compounds were obtained from a simple acylphloroglucinol scaffold. Highly enantioselective dearomatization was accomplished using a Trost ligand-palladium(0) complex. A computational DFT model was developed to rationalize observed enantioselectivities and revealed a key reactant-ligand hydrogen bonding interaction. Dearomatized products were used in visible light-mediated photocycloadditions and oxidative free radical cyclizations to obtain novel polycyclic chemotypes including tricyclo[4.3.1.01,4]decan-10-ones, bicyclo[3.2.1]octan-8-ones and highly-substituted cycloheptanones.
authors.affiliation: Department of Chemistry, Center for Molecular Discovery, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA).
authors.forename: Mikayo
authors.initials: M
authors.lastname: Hayashi
authors.affiliation: Department of Chemistry, Center for Molecular Discovery, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA), brownle@bu.edu.
authors.forename: Lauren E
authors.initials: LE
authors.lastname: Brown
authors.affiliation: Department of Chemistry, Center for Molecular Discovery, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA), porco@bu.edu.
authors.forename: John A
authors.initials: JA
authors.lastname: Porco
keywords: asymmetric catalysis; dearomatization; photocatalysis; polycycles; radical reactions