Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction

Journal of the American Chemical Society
Junpeng WangStephen L Craig

Abstract

Mechanical forces, applied via covalent polymer mechanochemistry, have been used to bias reaction pathways and activate otherwise inaccessible reactions. Here, single-molecule polymer mechanochemistry is used to induce the disrotatory outward ring opening of a cis-dialkyl substituted syn-chloro-gem-chlorofluorocyclopropane, in violation of the Woodward-Hoffmann-DePuy (WHD) rule. The forces required to trigger the anti-WHD pathway on the ∼100 ms time scale of the experiment are about 200 pN greater than those involved in the WHD favored process (1290 vs 1500 pN). The kinetics are complemented by tension trapping experiments that suggest that the reaction proceeds along a reaction pathway that generates substantial diradicaloid character.

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Citations

Aug 22, 2016·The Journal of Chemical Physics·Sanjiv K JhaGopinath Subramanian
Jan 13, 2017·ACS Nano·Hongbin Li, Gilbert C Walker
Mar 4, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Sergey Akbulatov, Roman Boulatov
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Apr 19, 2019·Chemical Science·Leopoldo Mejía, Ignacio Franco
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Jan 23, 2021·Journal of the American Chemical Society·Anton O RazgoniaevKatherine J Franz
Feb 6, 2021·Chemical Society Reviews·Yinjun ChenRint P Sijbesma
Jan 1, 2021·Journal of the American Chemical Society·Robert Nixon, Guillaume De Bo
Jun 8, 2021·Chemical Science·Yangju Lin, Stephen L Craig
Jul 27, 2021·Journal of the American Chemical Society·Matías HorstYan Xia
Dec 4, 2019·The Journal of Physical Chemistry. B·Shawn R LavoieTian Tang
Mar 7, 2020·Journal of the American Chemical Society·Min Zhang, Guillaume De Bo
Jul 10, 2019·Journal of the American Chemical Society·Yangju LinStephen L Craig
Sep 19, 2019·The Journal of Physical Chemistry. B·Yangju LinStephen L Craig
Nov 1, 2017·Journal of the American Chemical Society·Richard Stevenson, Guillaume De Bo
Sep 23, 2020·Journal of the American Chemical Society·Liqi WangRoss A Widenhoefer
Nov 8, 2018·Journal of the American Chemical Society·Yangju LinStephen L Craig
Sep 10, 2020·Journal of the American Chemical Society·Isabel M KleinMaxwell J Robb
Sep 30, 2021·Journal of the American Chemical Society·Qingkai QiXiaocun Lu
Sep 10, 2021·Angewandte Chemie·Sangmin Jung, Hyo Jae Yoon

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