title: Photoaffinity labeling via nitrenium ion chemistry: protonation of the nitrene derived from 4-amino-3-nitrophenyl azide to afford reactive nitrenium ion pairs.
abstract: Phenyl azides with powerful electron-donating substituents are known to deviate from the usual photochemical behavior of other phenyl azides. They do not undergo ring expansion but form basic nitrenes that protonate to form nitrenium ions. The photochemistry of the widely used photoaffinity labeling system 4-amino-3-nitrophenyl azide, 5, has been studied by transient absorption spectroscopy from femtosecond to microsecond time domains and from a theoretical perspective. The nitrene generation from azide 5 occurs on the S(2) surface, in violation of Kasha's rule. The resulting nitrene is a powerful base and abstracts protons extremely rapidly from a variety of sources to form a nitrenium ion. In methanol, this protonation occurs in about 5 ps, which is the fastest intermolecular protonation observed to date. Suitable proton sources include alcohols, amine salts, and even acidic C-H bonds such as acetonitrile. The resulting nitrenium ion is stabilized by the electron-donating 4-amino group to afford a diiminoquinone-like species that collapses relatively slowly to form the ultimate cross-linked product. In some cases in which the anion is a good hydride donor, cross-linking is replaced by reduction of the nitrenium ion to the corresponding amine.
authors.affiliation: Department of Chemistry and the Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, USA.
authors.forename: Valentyna
authors.initials: V
authors.lastname: Voskresenska
authors.forename: R Marshall
authors.initials: RM
authors.lastname: Wilson
authors.forename: Maxim
authors.initials: M
authors.lastname: Panov
authors.forename: Alexander N
authors.initials: AN
authors.lastname: Tarnovsky
authors.forename: Jeanette A
authors.initials: JA
authors.lastname: Krause
authors.forename: Shubham
authors.initials: S
authors.lastname: Vyas
authors.forename: Arthur H
authors.initials: AH
authors.lastname: Winter
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Hadad
mesh_terms: D001386:Azides / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D015394:Molecular Structure; D019920:Photoaffinity Labels / Q000737:chemistry*; D010777:Photochemistry; D011522:Protons
chemical_list: D001386:Azides; D007097:Imines; D007477:Ions; D019920:Photoaffinity Labels; D011522:Protons; C046309:3-nitrophenyl azide; C017621:phenylnitrene