THE PHOTOCHEMISTRY OF 3-NITROBENZOYL AND 4-NITROBENZOYL AZIDES: POSSIBLE REAGENTS FOR PHOTOAFFINITY LABELING |
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| Authors: | Ingrid Woelfle Björn Sauerwein Tom Autrey Gary B Schuster |
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| Institution: | Department of Chemistry, Roger Adams Laboratory, University of Illinois, Urbana, IL 61801, USA |
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| Abstract: | Abstract— The photochemistry of 3- and 4-nitrobenzoyl azides was studied to examine their suitability for use in photolabeling procedures. These aroyl azides absorb light in the near UV-spectral region. Their irradiation leads both to photo-Curtius rearrangement with formation of the analogous isocyan-ates and to generation of nitrenes by loss of nitrogen. The chemical and spectroscopic properties of the aroyl nitrenes indicate that they are singlets in their ground states. These singlet nitrenes insert rapidly into unactivated, aliphatic carbon-hydrogen bonds, trap nucleophiles, and add to olefins to form aziridines with retention of stereochemistry. Photolabeling agents based on these azides may offer some advantages over conventional agents for the labeling of lipophilic sites. |
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