General approach for the synthesis of chiral perylenequinones via catalytic enantioselective oxidative biaryl coupling.
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.
Mulrooney
Carol A
CA
Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
Li
Xiaolin
X
DiVirgilio
Evan S
ES
Kozlowski
Marisa C
MC
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
D011809:Quinones; D010569:Perylene