Stereospecific Furanosylations Catalyzed by Bis-thiourea Hydrogen-Bond Donors

We report a new method for stereoselective O-furanosylation reactions promoted by a precisely tailored bis-thiourea hydrogen-bond-donor catalyst. Furanosyl donors outfitted with an anomeric dialkylphosphate leaving group undergo substitution with high anomeric selectivity, providing access to the ch...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2020-02, Vol.142 (8), p.4061-4069
Main Authors: Mayfield, Andrew B, Metternich, Jan B, Trotta, Adam H, Jacobsen, Eric N
Format: Article
Language:English
Subjects:
Catalysis
Furans - chemistry
Hydrogen Bonding
Stereoisomerism
Thiourea - chemistry
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Summary:We report a new method for stereoselective O-furanosylation reactions promoted by a precisely tailored bis-thiourea hydrogen-bond-donor catalyst. Furanosyl donors outfitted with an anomeric dialkylphosphate leaving group undergo substitution with high anomeric selectivity, providing access to the challenging 1,2-cis substitution pattern with a range of alcohol acceptors. A variety of stereochemically distinct, benzyl-protected glycosyl donors were engaged successfully as substrates. Mechanistic studies support a stereospecific mechanism in which rate-determining substitution occurs from a catalyst–donor resting-state complex.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c00335