In a recent paper [N.S. Isaacs and A. Laila, J. Phys. Org. Chem. 7, 17
8 (1994)2] the volume profile for the cheletropic addition of sulphur
dioxide to a 1,3-diene (2,3-dimethylbuta-1,3-diene) indicated that a t
wo-step mechanism for this reaction, with a (4 + 2) cycloaddition at t
he S=O bond as the slow step followed by a rapid rearrangement of the
resultant sulpheno-lactone, cannot be ruled out. However, ab initio ca
lculations, at the MP2(FC)/6-31G//RHF/6-31G* level, show that such a
mechanism can be conclusively discarded.