A new approach to prepare α-selanyl-α,β-unsaturated thioesters from propargylthioalkynes and an electrophilic selenium species is reported. Pivotal is the intermediacy of a sulfur-stabilized vinyl cation, which is captured intramolecularly and ultimately enables 37 examples of the target compounds to be prepared in good yields. Computational studies shed light on the nature of intermediates in this transformation.
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