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A straightforward and scalable method for direct C–N bond formation is developed using primary sulfonamides and aliphatic aldehydes. The reaction proceeds efficiently within a catalytic system that comprises 0.3 equivalents of sodium iodide and 1.2 equivalents of sodium percarbonate, facilitating rapid synthesis of α-sulfonamido acetals with excellent functional group tolerance. This protocol demonstrates significant potential for medicinal chemistry applications, particularly in the derivatization of sulfa drugs into α-amino alcohols/esters.

Graphical abstract: Oxidative N-functionalization of primary sulfonamides with aliphatic aldehydes: a green synthesis of α-sulfonamido acetals

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