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Dyotropic rearrangement of alpha-lactone to beta-lactone: a computational study of small-ring halolactonisation


Reference:

Buchanan, J. G., Ruggiero, G. D. and Williams, I. H., 2008. Dyotropic rearrangement of alpha-lactone to beta-lactone: a computational study of small-ring halolactonisation. Organic and Biomolecular Chemistry, 6 (1), pp. 66-72.

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Abstract

Transition structures have been optimised using the B3LYP/ 6-31+G* density functional level method, in vacuum and in implicit (PCM) and explicit (DFT/MM) aqueous solvation, for the degenerate rearrangement of the alpha-lactone derived by the formal addition of Cl+ to acrylate anion and for the dyotropic rearrangement of this to the beta-lactone. Despite being lower in energy than the alpha-lactone, there is no direct pathway to the beta-lactone from the acrylate chloronium zwitterion, which is the transition structure for the degenerate rearrangement. This may be rationalised by consideration of the unfavorable angle of attack by the carboxylate nucleophile on the beta-position; attack on the alpha-position involves a less unfavorable angle. Formation of the beta-lactone may occur by means of a dyotropic rearrangement of the alpha-lactone. This involves a high energy barrier for the acrylate derived alpha-lactone, ;but dyotropic rearrangement of the beta,beta-dimethyl substituted alpha-lactone to the corresponding beta-lactone involves a much lower barrier, estimated at about 46 kJ mol(-1) in water, and is predicted to be a facile process.

Details

Item Type Articles
CreatorsBuchanan, J. G., Ruggiero, G. D. and Williams, I. H.
DOI10.1039/b714118a
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code4519
Additional InformationID number: ISI:000251580500017

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