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An unexpected copper catalyzed 'reduction' of an arylazide to amine through the formation of a nitrene intermediate
Hanjing Peng1, Kednerlin H Dornevil1, Alexander B Draganov1
1Department 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.
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.
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