Direct Access to Alkyl Amide N ‐Glycosides via Transition‐Metal‐Free Visible‐Light Carbonylation of Glycosylamines

Amide N ‐glycosides are privileged structural motifs found in glycoproteins, glycoconjugates, and numerous bioactive molecules, yet their preparation remains challenging because existing methods depend on hydrolytically sensitive intermediates or on forcing conditions that erode anomeric integrity. Herein, we report a transition‐metal‐free, visible‐light‐mediated carbonylative coupling of glycosylamines with unactivated alkyl iodides that provides a straightforward and stereoretentive route to structurally diverse alkyl amide N ‐glycosides. The transformation employs 4CzIPN as an inexpensive organic photocatalyst and SilaCOgen as a safer, bench‐stable carbon monoxide surrogate. A broad range of mono‐, di‐, and oligosaccharide‐derived glycosylamines, including anomeric and non‐anomeric glucosamine derivatives and a glycosyl sulfoximine, undergo efficient carbonylation, and the isolated products were assigned with retention of the anomeric configuration. The protocol is compatible with primary, secondary, and tertiary alkyl iodides, tolerates esters, N ‐Boc and N ‐Cbz carbamates, a cyclic ketal, and an aryl ether, and enables the late‐stage functionalization of complex natural‐product‐derived substrates. Its synthetic utility is further demonstrated by the direct incorporation of a ¹³ C‐labeled carbonyl group, which delivers isotopically labeled amide N ‐glycosides with 99.4% isotopic incorporation. This operationally simple strategy expands the synthetic toolbox for amide N ‐glycoside synthesis and provides access to carbohydrate‐based building blocks for glycochemistry and medicinal chemistry.