Mechanism and Stereoselectivity of the Stepwise 1,3-Dipolar Cycloadditions between a Thiocarbonyl Ylide and Electron-Deficient Dipolarophiles: A Computational Investigation

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.