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  • Title: Exo-selective Diels-Alder reactions of vinylazepines. Origin of divergent stereoselectivity in Diels-Alder reactions of vinylazepines, vinylpiperideines, and vinylcycloalkenes.
    Author: Boren B, Hirschi JS, Reibenspies JH, Tallant MD, Singleton DA, Sulikowski GA.
    Journal: J Org Chem; 2003 Nov 14; 68(23):8991-5. PubMed ID: 14604372.
    Abstract:
    Diels-Alder reactions of vinylazepines with N-phenylmaleimide afforded exclusively the exo cycloadduct, while high endo stereoselectivity was observed, as previously reported, in analogous reactions of vinylpiperideines. This curious contrast was confirmed by X-ray analysis of cycloadducts not susceptible to epimerization. The stereoselectivity of Diels-Alder reactions of vinylazepines, vinylpiperideines, and vinylcycloalkenes exhibits surprising divergence depending on the detailed diene structure, and DFT calculations (Becke3LYP) were undertaken to shed light on these observations. The model calculations correctly predict the major stereoisomers in these reactions, though they tend to significantly underestimate the stereoselectivity. The results suggest some general considerations in predicting or controlling the stereochemistry of this class of Diels-Alder reactions.
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