Unprotected C-Aryl Glycosides From Native Sugars via Glycosyl Sulfonyl Hydrazides: A Thermal Cap-and-Glycosylate
Shuai-Peng Gao1, Guo-Zhao Fan1, Shuai Liu1
1National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang, China.
Abstract:
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.
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