Unprotected C ‐Aryl Glycosides From Native Sugars via Glycosyl Sulfonyl Hydrazides: A Thermal Cap‐and‐Glycosylate Strategy

We report a thermal cap‐and‐glycosylate strategy for the direct, protecting‐group‐free synthesis of unprotected aryl C‐glycosides from native sugars, employing glycosyl sulfonyl hydrazides as glycosyl radical precursors under redox‐neutral nickel catalysis. This two‐step process avoids photoirradiation, chromatography, and external redox agents. 11 Unprotected monosaccharides react with high 1,2‐ trans selectivity, tolerating diverse functional groups and heteroarenes. The utility is showcased by two‐step assembly of gliflozin drugs, their analogues and Neopetrosin C. This platform positions glycosyl sulfonyl hydrazides as a versatile radical source and a scalable alternative to photoinduced C‐glycosylation.