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Photosensitized Thymine Dimerization via Delocalized Triplet Excited States
Authors:Paula Miro  Virginie Lhiaubet‐Vallet  M. Luisa Marin  Miguel A. Miranda
Affiliation:Instituto Universitario Mixto de Tecnología Química (UPV‐CSIC), Universitat Politècnica de València, Avenida de los Naranjos s/n, 46022 Valencia (Spain)
Abstract:A new mechanism of photosensitized formation of thymine (Thy) dimers is proposed, which involves generation of a delocalized triplet excited state as the key step. This is supported by chemical evidence obtained by combining one benzophenone and two Thy units with different degrees of freedom, whereby the photoreactivity is switched from a clean Paternò–Büchi reaction to a fully chemo‐, regio‐, and stereoselective [2+2] cycloaddition.
Keywords:dimerization  DNA damage  nucleobases  photochemistry  reaction mechanisms
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