Loading…
An unexpected copper catalyzed areductiona of an arylazide to amine through the formation of a nitrene intermediate
Azido nitrobenzoxadiazole (NBD) was observed to undergo a areductiona 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 solven...
Saved in:
Published in: | Tetrahedron 2013-06, Vol.69 (25), p.5079-5085 |
---|---|
Main Authors: | , , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
Summary: | Azido nitrobenzoxadiazole (NBD) was observed to undergo a areductiona 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 areductiona 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. |
---|---|
ISSN: | 0040-4020 |
DOI: | 10.1016/j.tet.2013.04.091 |