Radical intermediates in the photorearrangement of 3-hydroxyindolic nitrones

A number of 3-hydroxy substituted indolic nitrones were found to quantitatively photorearrange to (2-benzoylamino)phenyl ketones upon UV-A irradiation. EPR-Spin Trapping experiments suggest that the process, which is believed to proceed via the formation of an oxaziridine, follows a homolytic pathway. Although DFT calculations do not allow to totally exclude alternative routes involving singlet intermediates, they do provide support to the proposed homolytic mechanism, which would be driven by a 1,5-hydrogen transfer subsequent to the oxaziridine ring opening. When this hydrogen transfer was made impossible by methylation of the 3-OH group, a benzoxazine was isolated as the sole reaction product. (C) 2011 Elsevier Ltd. All rights reserved.