Materials Chemistry Commons^™

Photoaffinity Labeling Via Nitrenium Ion Chemistry: Protonation Of The Nitrene Derived From 4-Amino-3-Nitrophenyl Azide To Afford Reactive Nitrenium Ion Pairs, Valentyna Voskresenska, R. Marshall Wilson, Maxim Panov, Alexander N. Tarnovsky, Jeanette A. Krause, Shubham Vyas, Arthur Winter, Christopher M. Hadad

Arthur Winter

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 S2 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 …