Stereoselective Synthesis of Glycosyl Phosphonates from Saccharides Via Selenium-Catalyzed Dehydrogenations
Dang-Wei Qian1, Lan Ma1, Shang-Dong Yang1,2
1State Key Laboratory of Natural Product Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou 730000, China.
Abstract:
Glycosyl diphenylphosphonates are a type of glycosyl donor featuring a phosphorus-containing leaving group at the anomeric carbon, and their coupling reaction has been extensively studied in oligosaccharide synthesis. Herein, we have developed an efficient and green synthetic method for the direct dehydrogenative coupling of glucose derivatives with secondary phosphine oxides under ambient air, using a catalytic amount of diaryl diselenide. This method eliminates the need for glycosyl chlorides and phosphorochloridates, as well as preactivated reagents such as N-methylimidazole. Water is generated as the sole byproduct. The system exhibits broad compatibility with monosaccharides and furanose derivatives (e.g., glucose, mannose, and galactose), enabling the synthesis of glycosyl phosphonate compounds in high yields (up to 93%) and with excellent β-selectivity.
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