Sulfoxide-induced stereoselection in [1,5]-sigmatropic hydrogen shifts of vinylallenes. A computational study.

The sulfoxide-induced preference for a migrating trajectory in the vinylallene [1,5]-H sigmatropic shift (resulting in stereodefined trienes in the conceptual equivalent of torquoselectivity in electrocyclizations), originally reported by Okamura, has been computationally studied at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31++G(d,p) level. The face selectivity this group induces in the [1,5]-H shift is enhanced by bulky geminal substituents and is not reproduced by any of the other (more than 20) substituents tested. Analysis of transition-state geometries or charges and evaluation of steric effects did not show any correlation with the preferences. The origin of this selectivity is thought to lie in a secondary orbital interaction (SOI) involving the termini of the pericyclic array and the sulfinyl group which is only observed for this substituent. This secondary orbital interaction, arising from the favorable energies of the orbitals involved, is enhanced in the transition structure due to a better orbital overlap (piC2-C3-->sigma*C1-S), which correlates with a piC2-C3-->sigma*C6-H SOI, which is more important in the transition structure, that weakens the C-H bond, thus lowering the energy of the corresponding transition structure.