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A highly efficient and operationally simple method for the synthesis of β-sulfinyl alkenylsulfones through the BF3•OEt2-promoted reaction of alkynes and sodium sulfinates is developed, successfully avoiding the complicated anhydrous treatment before the reaction and greatly simplifying the reaction conditions. As a facile and selective access to the targets, it features good functional group compatibility, mild conditions, easily available starting materials, and excellent yields. Notably, the trace water in solvent plays a key role in promoting the reaction, which provides a more practical pathway for the utilization of BF3•OEt2 catalytic system.
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