Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways

Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways Full article

Journal

Journal of Organic Chemistry
ISSN: 1520-6904 , E-ISSN: 0022-3263

Output data

Year: 2022, Volume: 87, Number: 21, Pages: 13643-13652 Pages count : 10 DOI: 10.1021/acs.joc.2c01294

Authors

Yadykov Anton V. ¹ , Eremchenko Artem E. ^2,1 , Milosavljevic Aleksa ³ , Frontier Alison J. ³ , Shirinian Valerii Z. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
2	D. I. Mendeleev University of Chemical Technology of Russia, 125047 Moscow, Russian Federation
3	Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14611, United States

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.

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. V.87. N21. P.13643-13652. DOI: 10.1021/acs.joc.2c01294 WOS Scopus OpenAlex

Web of science:	WOS:000870179500001
Scopus:	2-s2.0-85141464899
OpenAlex:	W4304588614

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