DFT study on the regio- and stereoselectivity of the organocatalytic aza-Diels-Alder reaction of crotonaldehyde and cyclic 1-aza-1,3-butadiene
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The mechanism of 1,4-, 1,2-, and 3,4-cyclization reactions of cyclic 1-azadiene 1 with an organocatalyst 4 has been studied theoretically using DFT method. The reactions proceed in a stepwise fashion, with zwitterionic intermediates. The most favorable cyclization reaction takes place along the C–C pathway of the 1,4-cyclization reaction, under a combination of kinetic and thermodynamic control. The reaction is characterized by the nucleophilic attack of 4 (C5) to the electrophilic center of 1 (C1), leading to the formation of cycloadduct 6, which correctly explains the source of the regioselectivity.
KeywordsStepwise Amino-catalysis Regio- and stereoselectivity Density functional theory Cyclization reaction
The authors wish to acknowledge Dr. Louise S. Price, University College London, UK, for reading the manuscript and providing valuable suggestions.
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