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Liu, Richard

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Liu

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Richard

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Liu, Richard

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  • Publication
    Macrocyclic bis-thioureas catalyze stereospecific glycosylation reactions
    (American Association for the Advancement of Science (AAAS), 2017-01-12) Park, Yongho; Harper, Kaid; Kuhl, Nadine; Kwan, Eugene; Liu, Richard; Jacobsen, Eric
    Carbohydrates are involved in nearly all aspects of biochemistry, but their complex chemical structures present long-standing practical challenges to their synthesis. In particular, stereochemical outcomes in glycosylation reactions are highly dependent on the steric and electronic properties of coupling partners; thus, carbohydrate synthesis is not easily predictable. Here we report the discovery of a macrocyclic bis-thiourea derivative that catalyzes stereospecific invertive substitution pathways of glycosyl chlorides. The utility of the catalyst is demonstrated in the synthesis of trans-1,2-, cis-1,2-, and 2-deoxy-β-glycosides. Mechanistic studies are consistent with a cooperative mechanism in which an electrophile and a nucleophile are simultaneously activated to effect a stereospecific substitution reaction.