title: Chemoselective nitration of phenols with tert-butyl nitrite in solution and on solid support.
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.
authors.affiliation: Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, USA.
authors.forename: Dipankar
authors.initials: D
authors.lastname: Koley
authors.forename: Olvia C
authors.initials: OC
authors.lastname: Colón
authors.forename: Sergey N
authors.initials: SN
authors.lastname: Savinov
mesh_terms: D009573:Nitrites / Q000737:chemistry*; D010084:Oxidation-Reduction; D010447:Peptide Hydrolases / Q000378:metabolism; D010455:Peptides / Q000737:chemistry; D010636:Phenols / Q000737:chemistry*; D010942:Plant Viruses / Q000201:enzymology; D014443:Tyrosine / Q000737:chemistry*
chemical_list: D009573:Nitrites; D010455:Peptides; D010636:Phenols; D014443:Tyrosine; C024225:n-butyl nitrite; D010447:Peptide Hydrolases
references.citation: Protein Sci. 2007 Jul;16(7):1257-65
references.pmid: 17567746
references.citation: J Org Chem. 2005 Oct 28;70(22):9071-3
references.pmid: 16238357
references.citation: Anal Biochem. 1991 May 15;195(1):141-7
references.pmid: 1888010
references.citation: J Org Chem. 2001 Jan 12;66(1):35-40
references.pmid: 11429927
references.citation: Chem Res Toxicol. 2000 Dec;13(12):1287-93
references.pmid: 11123970
references.citation: J Med Chem. 1992 Jun 26;35(13):2384-91
references.pmid: 1320122
references.citation: J Org Chem. 2005 Feb 18;70(4):1364-8
references.pmid: 15704971
references.citation: J Org Chem. 2002 May 3;67(9):2942-7
references.pmid: 11975550
references.citation: Biochemistry. 1974 Jun 4;13(12):2656-62
references.pmid: 4151620
references.citation: J Phys Chem A. 2005 May 19;109(19):4261-6
references.pmid: 16833754
references.citation: Bioorg Med Chem Lett. 2001 Jul 23;11(14):1843-9
references.pmid: 11459644
references.citation: Protein Sci. 2006 May;15(5):976-86
references.pmid: 16641485
references.citation: Chem Rev. 2006 May;106(5):1769-84
references.pmid: 16683754
references.citation: Eur J Biochem. 1970 Feb;12(2):250-7
references.pmid: 5466620
references.citation: Angew Chem Int Ed Engl. 2006 Jul 10;45(28):4562-89
references.pmid: 16819760
references.citation: Biochem Biophys Res Commun. 2002 Jun 28;294(5):949-55
references.pmid: 12074568