Herein, we report our approach for a Meyer-Schuster type rearrangement to access α-iodo α,β-unsaturated thioesters from propargyl thioalkynes using a silver(I) catalyst and N-iodosuccinimide as electrophilic iodine source. The reaction proceeds smoothly for a range of propargyl thioalkyne thus delivering tri- and tetrasubstituted olefins in good yields and, for a number of examples, (Z)-selectivity. The silver catalyst presumably plays a dual role involving both the activation of the π-system by the alkynophilic Ag(I) and the activation of the NIS, ultimately leading to a sulfur-stabilized vinyl cation/ketenethionium intermediate. This reactive intermediate is trapped intramolecularly to yield an oxetane which then readily undergoes decomposition to deliver the final product

You have access to this article

Please wait while we load your content... Something went wrong. Try again?