Redirecting a Diels-Alder Reaction toward (2 + 2)-Cycloaddition
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Updated: Nov 16, 2025

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Maria V Panova1, Michael G Medvedev1, Maksim A Mar'yasov2
1N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russian Federation.
Abstract:
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.
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