Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes

Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes
Maurizio Fagnoni, Stefano Protti, Angelo Albini, Davide Ravelli, Chiara Pedroli
The reactivity of α,n-didehydrotoluenes (DHTs) in protic media (organic/aqueous mixtures) was explored by means of a combined computational and experimental approach. These intermediates were generated via a photoinduced double elimination process occurring in (chlorobenzyl)trimethylsilanes and led to the formation of a varied products distribution, depending on the isomer tested. Irradiation of ortho- and para-derivatives resulted, respectively, in the formation of triplet α,2- and α,4-DHTs, whose diradical reactivity led to both radical and polar products. On the other hand, irradiation of the meta-precursor led to the singlet α,3-DHT isomer. The latter showed a marked preference for the formation of polar products and this was rationalized, as supported by computational evidence, via the involvement of a zwitterionic species arising through interaction of the nucleophilic solvent with the benzylic position of the DHT.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00610

DOI: 10.1021/acs.joc.7b00610

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