Synthesis of Functionalized β-Keto Arylthioethers by the Aryne Induced [2,3] Stevens Rearrangement of Allylthioethers

A mild and transition-metal-free synthesis of beta-keto arylthioethers has been developed by the aryne triggered [2,3] Stevens rearrangement of allylthioethers. The key sulfur ylide intermediate for the rearrangement was formed by the S-arylation of allylthioethers with arynes generated from 2-(trimethylsilyl)aryl triflates using CsF. Later, the reaction products are converted into valuable heterocycles in two steps.