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An effective method for the synthesis of multi-substituted β-keto thioethers via Stevens rearrangement of simple β-keto thioethers with arynes has been developed. In these reactions, successive C–S/C–H/C–C bonds were formed in one pot under mild and transition-metal free conditions to afford multi-substituted β-keto thioethers in moderate to good yields.

Graphical abstract: Stevens rearrangement of thioethers with arynes: a facile access to multi-substituted β-keto thioethers

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