Azido-NBD was observed to undergo a �reduction� reaction in the absence of an obvious reducing agent, leading to amine formation. With DMSO as the solvent, a sulfoxide conjugate was also formed. The ratio of these two products is temperature- and solvent-dependent, with the addition of water significantly enhancing the ratio of the �reduction� product. Two reaction intermediates of the azido-NBD reaction in DMSO are trapped and characterized by low temperature EPR spectroscopy. One is an organic free radical (S = 1/2) and the other is a triplet nitrene (S = 1) species. Addition of water significantly reduces the free radical signal intensity and increases the intensity of the triplet EPR signal. In DMF, the �reduction� product is the predominate product. A metal-bound triplet is observed and the free radical signal is suppressed. A mechanism leading to the unusual �reduction� product is proposed based on the characterized free radical and triplet intermediates.

Unusual and facile “reduction” of an arylazide to amine through the formation of a triplet nitrene intermediate

241st National Meeting (2011)

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