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.