title: General approach for the synthesis of chiral perylenequinones via catalytic enantioselective oxidative biaryl coupling.
abstract: By using oxygen as the terminal oxidant, copper complexes derived from chiral 1,5-diaza-cis-decalin catalyze the enantioselective oxidative biaryl coupling of highly functionalized naphthols to provide octa- and decasubstituted binaphthalenes with high selectivity (86-90% ee). Products containing very electron-rich naphthalenes were prone to epimerization under the reaction conditions. This epimerization could be suppressed by employing naphthol starting materials with phenol protecting groups that attenuated the electron-rich nature of the naphthalenes. Direct oxidation of the resultant chiral 1,1'-binaphthol framework completed the first asymmetric synthesis of a perylenequinone containing only an axial chirality element.
authors.affiliation: Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Carol A
authors.initials: CA
authors.lastname: Mulrooney
authors.forename: Xiaolin
authors.initials: X
authors.lastname: Li
authors.forename: Evan S
authors.initials: ES
authors.lastname: DiVirgilio
authors.forename: Marisa C
authors.initials: MC
authors.lastname: Kozlowski
mesh_terms: D002384:Catalysis; D007700:Kinetics; D010084:Oxidation-Reduction; D010569:Perylene / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D011809:Quinones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D011809:Quinones; D010569:Perylene