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The [4+3] annulation reaction of crotonate-derived sulfur ylides with thioaurones has, for the first time, been reported using NaH as the base. A diverse array of 2,5-dihydrobenzo[4,5]thieno[3,2-b]oxepines is obtained in good to excellent yields. The proposed mechanism is investigated and supported by DFT calculations.

Graphical abstract: NaH promoted [4+3] annulation of crotonate-derived sulfur ylides with thioaurones: synthesis of 2,5-dihydrobenzo[4,5]thieno[3,2-b]oxepines

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