Mechanism and stereoselectivity of the stepwise 1,3-dipolar cycloadditions between a thiocarbonyl ylide and electron-deficient dipolarophiles: A computational investigation

Abstract

The 1,3-dipolar cycloadditions of a thiocarbonyl ylide to dimethyl 2,3-dicyanofumarate and 2,3-dicyanomaleate have been studied with DFT computations. The first C-C bond is formed via an anti attack to produce a very polar, zwitterionic diradical. The low stereoselectivity of the reaction was found to arise from rotations about single bonds in the intermediates that compete with cyclization. A distortion-interaction energy analysis was performed to compare the stepwise and concerted mechanisms, and to explain why the stepwise mechanism is favored in this unusual case. © 2010 American Chemical Society.