Redirecting a Diels–Alder Reaction toward (2 + 2)-Cycloaddition

Redirecting a Diels–Alder Reaction toward (2 + 2)-Cycloaddition Full article

Journal

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

Output data

Year: 2021, Volume: 86, Number: 6, Pages: 4398-4404 Pages count : 7 DOI: 10.1021/acs.joc.0c02386

Authors

Panova Maria V. ¹ , Medvedev Michael G. ¹ , Mar’yasov Maksim A. ² , Lyssenko Konstantin A. ^3,4 , Nasakin Oleg E. ²

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russian Federation
2	I. N. Ul’yanov Chuvash State University, Moskovskii Prospekt 15, Cheboksary 428015, Russian Federation
3	Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow 119991, Russian Federation
4	Plekhanov Russian University of Economics, Stremyannyi pereulok 36, Moscow 117997, Russian Federation

Recently, reactions of allylidenhydrazones with tetracyanoethylene were found to lead to cyclobutanes—products of usually unfavorable (2 + 2) cycloaddition. Herein we computationally demonstrate that the (4 + 2) product of this reaction is severely destabilized by incomplete C–N bond formation, arising from a complex interplay of substituent electronic effects. We show how destabilization of a single bond in the front-runner product averts its formation and redirects chemical reaction toward an uncharacteristic pathway.

Panova M.V. , Medvedev M.G. , Mar’yasov M.A. , Lyssenko K.A. , Nasakin O.E.
Redirecting a Diels–Alder Reaction toward (2 + 2)-Cycloaddition
Journal of Organic Chemistry. 2021. V.86. N6. P.4398-4404. DOI: 10.1021/acs.joc.0c02386 WOS Scopus OpenAlex

≡ Web of science:	WOS:000631442900003
≡ Scopus:	2-s2.0-85103337165
≡ OpenAlex:	W3132900949