Journal of Organic Chemistry, volume 87, issue 21, pages 13643-13652
Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways
Yadykov Anton V
1
,
Eremchenko Artem E
1, 2
,
3
Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14611, United States
|
Publication type: Journal Article
Publication date: 2022-10-11
Journal:
Journal of Organic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 3.6
ISSN: 00223263, 15206904
Organic Chemistry
Abstract
This work describes an acid-promoted cyclization of triaryldivinyl ketones containing a thiophene moiety in the α-position. Two cyclization pathways are accessible: one a 4π-Nazarov cyclization and the other we propose to proceed through a 6π electrocyclic mechanism. The relative proportion of products from these divergent pathways is affected by reaction conditions and steric bulk in the substrate. We present experimental and computational evidence that when using HCl in dioxane, the 4π-conrotatory electrocyclization is more favorable, whereas GaCl3 in methylene chloride shifts the chemoselectivity toward a putative 6π-disrotatory electrocyclization. DFT calculations suggest that a complex interplay between kinetic and thermodynamic factors is implicated in the chemodivergent behavior.
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Yadykov A. V. et al. Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways // Journal of Organic Chemistry. 2022. Vol. 87. No. 21. pp. 13643-13652.
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Yadykov A. V., Eremchenko A. E., Milosavljevic A., Frontier A. J., Shirinian V. Z. Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways // Journal of Organic Chemistry. 2022. Vol. 87. No. 21. pp. 13643-13652.
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TY - JOUR
DO - 10.1021/acs.joc.2c01294
UR - https://doi.org/10.1021%2Facs.joc.2c01294
TI - Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways
T2 - Journal of Organic Chemistry
AU - Yadykov, Anton V
AU - Eremchenko, Artem E
AU - Milosavljevic, Aleksa
AU - Frontier, Alison J.
AU - Shirinian, V. Z.
PY - 2022
DA - 2022/10/11 00:00:00
PB - American Chemical Society (ACS)
SP - 13643-13652
IS - 21
VL - 87
SN - 0022-3263
SN - 1520-6904
ER -
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@article{2022_Yadykov,
author = {Anton V Yadykov and Artem E Eremchenko and Aleksa Milosavljevic and Alison J. Frontier and V. Z. Shirinian},
title = {Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways},
journal = {Journal of Organic Chemistry},
year = {2022},
volume = {87},
publisher = {American Chemical Society (ACS)},
month = {oct},
url = {https://doi.org/10.1021%2Facs.joc.2c01294},
number = {21},
pages = {13643--13652},
doi = {10.1021/acs.joc.2c01294}
}
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Yadykov, Anton V., et al. “Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways.” Journal of Organic Chemistry, vol. 87, no. 21, Oct. 2022, pp. 13643-13652. https://doi.org/10.1021%2Facs.joc.2c01294.