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. 2009 Sep 17;11(18):4172-5.
doi: 10.1021/ol901731w.

Chemoselective nitration of phenols with tert-butyl nitrite in solution and on solid support

Dipankar Koley  1 , Olvia C Colón, Sergey N Savinov
Affiliations

Chemoselective nitration of phenols with tert-butyl nitrite in solution and on solid support

Dipankar Koley et al. Org Lett. .

Abstract

tert-Butyl nitrite was identified as a safe and chemoselective nitrating agent that provides preferentially mononitro derivatives of phenolic substrates in the presence of potentially competitive functional groups. On the basis of our control experiments, we propose that the reaction proceeds through the formation of O-nitrosyl intermediates prior to C-nitration via homolysis and oxidation. The reported nitration method is compatible with tyrosine-containing peptides on solid support in the synthesis of fluorogenic substrates for characterization of proteases.

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Figures

Scheme 1
Scheme 1
Nitration of tyrosine derivatives with t-BuONO.
Scheme 2
Scheme 2
Mechanistic analysis and proposed pathway for the nitration reaction with t-BuONO.
Scheme 3
Scheme 3
On-bead nitration and synthesis of a fluorogenic peptide.
See this image and copyright information in PMC

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