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Trends in Photochemistry & Photobiology   Volumes    Volume 14 
Photoreactivity of N-acetyl-7-nitroindolines – Unraveling the mechanism by computation
Jose E. Mendez, Nathan J. Westfall, Katja Michael, Carl W. Dirk
Pages: 75 - 91
Number of pages: 17
Trends in Photochemistry & Photobiology
Volume 14 

Copyright © 2012 Research Trends. All rights reserved

Photo-cleavable N-acyl-7-nitroindolines serve as a tool for the acylation of various nucleophiles. The mechanism by which the acylating species, the nitronic anhydride is formed, is not well understood. Reported here is a semiempirical AMPAC study of the reaction pathway in the ground and excited states. Results suggest an as yet experimentally unobserved ground state concerted suprafacial 1,5-sigmatropic shift pathway for the formation of the nitronic anhydride. The previously experimentally observed excited state pathway is considerably more complex. A concerted antarafacial shift is expected. However, on the S1 (lowest singlet excited state) manifold, the reaction appears to involve a shallow intermediate before proceeding by a hypothesized S1 to S0 (ground singlet) state crossing to the transition state for the concerted S0 shift, from which it likely proceeds onto a suprafacial shift to the nitronic anhydride. Triplet state behavior is explored and this system may possess a conical intersection of S0/S1/T1 potential energy surfaces. Further results explain the reactivity of the nitronic anhydride toward nucleophiles, as well as its susceptibility to protons, providing a complete mechanistic picture to explain the reaction behavior found by us and others. 
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