title: Copper-Catalyzed Aerobic Oxidative Amidation of Benzyl Alcohols.
abstract: A Cu-catalyzed synthesis of amides from alcohols and secondary amines using the oxygen in air as the terminal oxidant has been developed. The methodology is operationally simple requiring no high pressure equipment or handling of pure oxygen. The commercially available, nonprecious metal catalyst, Cu(phen)Cl2, in conjunction with di-tert-butyl hydrazine dicarboxylate and an inorganic base provides a variety of benzamides in moderate to excellent yields. The pKaof amine conjugate acid and electronics of alcohol were shown to impact the selection of base for optimal reactivity. A mechanism consistent with the observed reactivity trends, KIE, and Hammett study is proposed.
authors.affiliation: Process Research and Development, AbbVie Inc. , 1 North Waukegan Road, North Chicago, Illinois 60064, United States.
authors.forename: Scott W
authors.initials: SW
authors.lastname: Krabbe
authors.affiliation: Process Research and Development, AbbVie Inc. , 1 North Waukegan Road, North Chicago, Illinois 60064, United States.
authors.forename: Vincent S
authors.initials: VS
authors.lastname: Chan
authors.affiliation: Process Research and Development, AbbVie Inc. , 1 North Waukegan Road, North Chicago, Illinois 60064, United States.
authors.forename: Thaddeus S
authors.initials: TS
authors.lastname: Franczyk
authors.affiliation: Process Research and Development, AbbVie Inc. , 1 North Waukegan Road, North Chicago, Illinois 60064, United States.
authors.forename: Shashank
authors.initials: S
authors.lastname: Shekhar
authors.affiliation: Discovery Chemistry and Technology, AbbVie Inc. , 1 North Waukegan Road, North Chicago, Illinois 60064, United States.
authors.forename: José G
authors.initials: JG
authors.lastname: Napolitano
authors.affiliation: Discovery Chemistry and Technology, AbbVie Inc. , 1 North Waukegan Road, North Chicago, Illinois 60064, United States.
authors.forename: Carmina A
authors.initials: CA
authors.lastname: Presto
authors.affiliation: Process Research and Development, AbbVie Inc. , 1 North Waukegan Road, North Chicago, Illinois 60064, United States.
authors.forename: Justin A
authors.initials: JA
authors.lastname: Simanis