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An unprecedented construction of benzo[d][1,3]oxathiin-4-ones through skeletal editing of benzodithiol-3-ones is described herein, which represents the first example of swapping from an S atom to C–O entities. This organic phosphine-promoted skeletal editing of benzodithiol-3-ones enables the forging of a range of benzo[d][1,3]oxathiin-4-ones by using aldehydes as readily available cyclization partners. This novel skeletal editing strategy is distinguished by mild conditions, no need for inert gas protection, convenient operation, decent yields and good functional group compatibility.

Graphical abstract: Skeletal editing of benzodithiol-3-ones for the assembly of benzo[d][1,3]oxathiin-4-ones

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