Theoretical study of the mechanism of high-pressure induced 1,3-dipolar cycloadditions of azides with electron-rich olefins

The high-pressure induced 1,3-dipolar cycloadditions of azides with electron-rich olefins have been studied by means of density functional theory (DFT) method. It is shown that high-pressure could induce the 1,3-dipolar cycloaddition of azides not only with electron-deficient olefins but also with electron-rich ones. The results derived from the theoretical calculations also indicate that the concerted mechanism is both kinetically and thermodynamically preferred to the stepwise one. In addition, the solvent effects on the stability of the products and transition states are taken into account, and the comparison of the calculated results between the 1,3-dipolar cycloadditions of azides with electron-deficient olefins and electron-rich ones is employed. (c) 2007 Elsevier B.V. All rights reserved.