Département de chimie moléculaire

Theor. calcns. at the DFT level indicate that the reaction of a nitrone with a silyl ketene acetal proceeds, contrary to previous suggestions, through a classical 1,3-dipolar cycloaddn., followed by a silyl group transfer step to give the open-chain product. Introduction of a diffuse basis set is necessary to describe nitrones properly. The influence of a Lewis acid, ZnCl2, was studied; the most striking effect of the Lewis acid is essentially to eliminate the activation energy barrier in the first step. [on SciFinder(R)]