Understanding the mechanism of the 1,3-dipolar cycloaddition reaction between a thioformaldehyde S-oxide and cyclobutadiene: Competition between the stepwise and concerted routes

Changing the mechanism of the widely used 1,3-dipolar cycloaddition reaction from its usual asynchronous one-step pattern to the rarely observed stepwise form leads to the emergence of intermediates, side products, and other impurities. Thus, it is crucial to determine the nature of the mechanism of the 1,3-dipolar cycloaddition reaction between a special 1,3-dipole and a specified dipolarophile (by theoretical methods) before using them for synthesizing a desired product. In this study, therefore, we have investigated the possibility of some probable intermediates emergence in the 1,3-dipolar cycloaddition reaction between cyclobutadiene and thioformaldehyde S-oxide. The results showed that emergence of Int (B) (−52.1 kcal mol−1) via transition state (B-1) is favorable both thermodynamically and kinetically (in comparison with all other stepwise routes). That is, developing probable impurities should not be neglected at least in the cases of the reactions between some thioformaldehyde S-oxide and some dipolarophiles.