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Cethrene: The Chameleon of Woodward–Hoffmann Rules

Cite this: J. Org. Chem. 2018, 83, 8, 4769–4774
Publication Date (Web):March 19, 2018
https://doi.org/10.1021/acs.joc.8b00656
Copyright © 2018 American Chemical Society

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    Abstract

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    We demonstrate that the electrocyclic (EC) ring-closure of cethrene in solution proceeds in a conrotatory mode both thermally and photochemically. The facile photochemical EC process promises that cethrene can serve as an efficient chiroptical switch operated solely by light. As for the thermally activated EC reaction, a low reaction barrier and a solvation effect on the EC rate indicate that the C2-symmetric pathway predicted by DFT calculations might not be the correct mechanism. Instead, we argue that the molecular symmetry decreases along the reaction coordinate as a consequence of the low-energy singlet excited state in this diradicaloid molecule, which might lead to a lower activation energy in accord with that determined through kinetic studies. Cethrene, therefore, represents a thought-provoking molecular chameleon of the Woodward–Hoffmann rules that puts our chemical concepts and intuition to test.

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