An unexpected copper catalyzed 'reduction' of an arylazide to amine through the formation of a nitrene intermediate

Hanjing Peng, Kednerlin H. Dornevil, Alexander B. Draganov, Weixuan Chen, Chaofeng Dai, William H. Nelson, Aimin Liu, Binghe Wang

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish (US)
Pages (from-to)5079-5085
Number of pages7
JournalTetrahedron
Volume69
Issue number25
DOIs
StatePublished - Jun 24 2013
Externally publishedYes

Keywords

  • Azide
  • EPR
  • NBD
  • Nitrene
  • Reduction

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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