Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction.
Publication
, Journal Article
Wang, J; Kouznetsova, TB; Craig, SL
Published in: Journal of the American Chemical Society
September 2015
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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Published In
Journal of the American Chemical Society
DOI
EISSN
1520-5126
ISSN
0002-7863
Publication Date
September 2015
Volume
137
Issue
36
Start / End Page
11554 / 11557
Related Subject Headings
- General Chemistry
- 40 Engineering
- 34 Chemical sciences
- 03 Chemical Sciences
Citation
APA
Chicago
ICMJE
MLA
NLM
Wang, J., Kouznetsova, T. B., & Craig, S. L. (2015). Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction. Journal of the American Chemical Society, 137(36), 11554–11557. https://doi.org/10.1021/jacs.5b06168
Wang, Junpeng, Tatiana B. Kouznetsova, and Stephen L. Craig. “Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction.” Journal of the American Chemical Society 137, no. 36 (September 2015): 11554–57. https://doi.org/10.1021/jacs.5b06168.
Wang J, Kouznetsova TB, Craig SL. Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction. Journal of the American Chemical Society. 2015 Sep;137(36):11554–7.
Wang, Junpeng, et al. “Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction.” Journal of the American Chemical Society, vol. 137, no. 36, Sept. 2015, pp. 11554–57. Epmc, doi:10.1021/jacs.5b06168.
Wang J, Kouznetsova TB, Craig SL. Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction. Journal of the American Chemical Society. 2015 Sep;137(36):11554–11557.
Published In
Journal of the American Chemical Society
DOI
EISSN
1520-5126
ISSN
0002-7863
Publication Date
September 2015
Volume
137
Issue
36
Start / End Page
11554 / 11557
Related Subject Headings
- General Chemistry
- 40 Engineering
- 34 Chemical sciences
- 03 Chemical Sciences