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Experimental and computational studies of α‐lactones: Structure and bonding in the three‐membered ring
Author(s) -
Buchanan J. Grant,
Charlton Michael H.,
Mahon Mary F.,
Robinson James J.,
Ruggiero Giuseppe D.,
Williams Ian H.
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.526
Subject(s) - chemistry , aqueous solution , molecule , ring (chemistry) , atoms in molecules , computational chemistry , density functional theory , lactone , crystallography , stereochemistry , organic chemistry
Crystallographic analysis of the bromo‐β‐lactones obtained by addition of bromine to aqueous solutions of disodium 2,3‐dimethylmaleate and 2,3‐dimethylfumarate reveals stereochemistries ( 4 from 1 , and 3 from 2 ) opposite to those originally assigned ( 3 from 1 , and 4 from 2 ). Specifically, the maleate leads to a bromo‐β‐lactone with the methyl groups in a trans relationship, whereas the fumarate leads to the corresponding cis isomer. To account for this observation, we suggest that the first‐formed intermediate in each case is an α‐lactone. B3LYP/6–31 + G(d) calculations in PCM water indicate that the cyclic chloronium and bromonium adducts of acrylate anion are not intermediates but transition structures for the degenerate rearrangement of halomethyl‐α‐lactones. Bader analysis of MP2/6–31 + G(d,p) electron density distributions indicates that oxiranone possesses considerable ionic character in the endocyclic C α —O n bond. In PCM water there is neither a ring critical point nor a bond critical point for C α —O n , although geometrically the molecule still possesses an acute‐angled three‐membered ring with a C α CO n angle of only 69°. Combined quantum/classical calculations for B3LYP/6–31 + G(d) oxiranone surrounded by about 600 explicit TIP3P water molecules indicate that the cyclic structure is an energy minimum in aqueous solution, and Bader analysis gives a result similar to that from the continuum model. Copyright © 2002 John Wiley & Sons, Ltd.