title: An unexpected copper catalyzed 'reduction' of an arylazide to amine through the formation of a nitrene intermediate.
abstract: Azido nitrobenzoxadiazole (NBD) was observed to undergo a 'reduction' reaction in the absence of an obvious reducing agent, leading to amine formation. In the presence of an excess amount of DMSO, a sulfoxide conjugate was also formed. The ratio of these two products was both temperature- and solvent-dependent, with the addition of water significantly enhancing the ratio of the 'reduction' product. Two intermediates of the azido-NBD reaction in DMSO were trapped and characterized by low-temperature EPR spectroscopy. One was an organic free radical (S=1/2) and another was a triplet nitrene (S=1) species. A mechanism was proposed based on the characterized free radical and triplet intermediates.
authors.affiliation: Department of Chemistry, Center for Biotechnology and Drug Design, and Center for Diagnostics and Therapeutics, Georgia State University, P.O. Box 3965, Atlanta, Georgia 30302-3965, USA.
authors.forename: Hanjing
authors.initials: H
authors.lastname: Peng
authors.affiliation: Department of Chemistry, Center for Biotechnology and Drug Design, and Center for Diagnostics and Therapeutics, Georgia State University, P.O. Box 3965, Atlanta, Georgia 30302-3965, USA.
authors.forename: Kednerlin H
authors.initials: KH
authors.lastname: Dornevil
authors.affiliation: Department of Chemistry, Center for Biotechnology and Drug Design, and Center for Diagnostics and Therapeutics, Georgia State University, P.O. Box 3965, Atlanta, Georgia 30302-3965, USA.
authors.forename: Alexander B
authors.initials: AB
authors.lastname: Draganov
authors.affiliation: Department of Chemistry, Center for Biotechnology and Drug Design, and Center for Diagnostics and Therapeutics, Georgia State University, P.O. Box 3965, Atlanta, Georgia 30302-3965, USA.
authors.forename: Weixuan
authors.initials: W
authors.lastname: Chen
authors.affiliation: Department of Chemistry, Center for Biotechnology and Drug Design, and Center for Diagnostics and Therapeutics, Georgia State University, P.O. Box 3965, Atlanta, Georgia 30302-3965, USA.
authors.forename: Chaofeng
authors.initials: C
authors.lastname: Dai
authors.affiliation: Department of Physics and Astronomy, Georgia State University, P.O. Box 4106, Atlanta, Georgia 30302-4106, USA.
authors.forename: William H
authors.initials: WH
authors.lastname: Nelson
authors.affiliation: Department of Chemistry, Center for Biotechnology and Drug Design, and Center for Diagnostics and Therapeutics, Georgia State University, P.O. Box 3965, Atlanta, Georgia 30302-3965, USA.
authors.forename: Aimin
authors.initials: A
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Center for Biotechnology and Drug Design, and Center for Diagnostics and Therapeutics, Georgia State University, P.O. Box 3965, Atlanta, Georgia 30302-3965, USA.
authors.forename: Binghe
authors.initials: B
authors.lastname: Wang
keywords: Azide; EPR; NBD; Nitrene; Reduction