A Computational and Experimental Investigation of the Diels-Alder Cycloadditions of Halogen Substituted 2(H)-pyran-2-one
Bearpark, M.J. Ndibwami, A.
Bearpark, M.J.
Ndibwami, A.
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2003
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Abstract
4-Chloro-2(H)-pyran-2-one undergoes thermal DielsāAlder cycloaddition with electron-deficient dienophiles to afford, without any significant selectivity, 6-endo- and 5-endo-substituted bicyclic lactone cycloadducts. In contrast to 3- and 5-bromo-2(H)-pyran-2-one, 4-chloro-2(H)-pyran-2-one does not undergo thermal cycloadditions with electron-rich dienophiles. The regio- and stereochemical preferences of the cycloadditions of 4-chloro-2(H)-pyran-2-one and other related 2(H)-pyran-2-ones are investigated computationally. Calculations were carried out on the transition states leading to the four possible regio- and stereoisomeric cycloadducts using density functional theory (B3LYP/6-31G*). These studies allow prediction of the regio- and stereoselectivity in these reactions which are in line with experimental observations.
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Afarinkia, K., Bearpark, M. J., Ndibwami, A. (2003) A Computational and Experimental Investigation of the Diels-Alder Cycloadditions of Halogen Substituted 2(H)-pyran-2-one. The Journal of Organic Chemistry. 68 (19): 7158-7166.
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