title: Dearomative dihydroxylation with arenophiles.
abstract: Aromatic hydrocarbons are some of the most elementary feedstock chemicals, produced annually on a million metric ton scale, and are used in the production of polymers, paints, agrochemicals and pharmaceuticals. Dearomatization reactions convert simple, readily available arenes into more complex molecules with broader potential utility, however, despite substantial progress and achievements in this field, there are relatively few methods for the dearomatization of simple arenes that also selectively introduce functionality. Here we describe a new dearomatization process that involves visible-light activation of small heteroatom-containing organic molecules-arenophiles-that results in their para-cycloaddition with a variety of aromatic compounds. The approach uses N-N-arenophiles to enable dearomative dihydroxylation and diaminodihydroxylation of simple arenes. This strategy provides direct and selective access to highly functionalized cyclohexenes and cyclohexadienes and is orthogonal to existing chemical and biological dearomatization processes. Finally, we demonstrate the synthetic utility of this strategy with the concise synthesis of several biologically active compounds and natural products.
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Emma H
authors.initials: EH
authors.lastname: Southgate
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Jola
authors.initials: J
authors.lastname: Pospech
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Junkai
authors.initials: J
authors.lastname: Fu
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Daniel R
authors.initials: DR
authors.lastname: Holycross
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: David
authors.initials: D
authors.lastname: Sarlah
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D061565:Cycloaddition Reaction; D003511:Cyclohexanols / Q000138:chemical synthesis*; D003514:Cyclohexylamines / Q000138:chemical synthesis; D006900:Hydroxylation; D008027:Light; D015394:Molecular Structure; D010636:Phenols / Q000138:chemical synthesis
chemical_list: D001391:Azo Compounds; D001555:Benzene Derivatives; D003511:Cyclohexanols; D003514:Cyclohexylamines; C544043:MK7607; D010636:Phenols; C545152:conduramine A-1