The Walden cycle revisited: a computational study of competitive ring closure to alpha- and beta-lactones |
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Authors: | Buchanan J Grant Diggle Richard A Ruggiero Giuseppe D Williams Ian H |
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Institution: | Department of Chemistry, University of Bath, UK. |
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Abstract: | The text-book Walden cycle which interconverts the stereochemical configurations of chlorosuccinic and malic acids involves a beta-lactone intermediate in preference to an alpha-lactone intermediate because the O(nuc) C Cl angle in the transition structure for the former (174 degrees) is more favourable than that for the latter (139 degrees), as determined by PCM(epsilon = 78.4)/B3LYP/6-31+G* calculations; the smaller ring-strain energy of the beta-lactone contributes little to the reactivity difference. |
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