Stereoselective β-mannosylation has been recognized as one of the greatest challenges of carbohydrate chemistry. Herein, we described a practical method for stereoselective construction of β-mannosides by using a 2,6-lactone-bridged thiomannosyl donor through the remote acyl-group participation as well as the steric effect of O-4 substituent. The two effects are enabled through the conversion of a regular mannopyranosyl 4 C1 conformation into a 2,6-lactone bridged conformation. The lactone donor could be readily prepared in three steps on a gram scale and the β-mannosylation proceeded smoothly with high stereoselectivity for primary, secondary and tertiary alcohol acceptors. In addition, this strategy was successfully applied to the synthesis of a naturally occurring trisaccharide.
Keywords: 2,6-lactone bridge; mannosylation; remote acyl group participation; stereoselectivity; steric effect.
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