Cyanomethyl Ether as an Orthogonal Participating Group for Stereoselective Synthesis of 1,2-trans-β‑O‑Glycosides

Stereoselective formation of glycosidic linkages has been the prime focus for contemporary carbohydrate chemistry. Herein, we report cyanomethyl (CNMe) ether as an efficient and effective participating orthogonal protecting group for the stereoselective synthesis of 1,2-trans-β-O-glycosides. The par...

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Bibliographic Details
Published in:Journal of organic chemistry 2020-08, Vol.85 (15), p.9955-9968
Main Authors: Molla, Mosidur Rahaman, Das, Pradip, Guleria, Kanika, Subramanian, Ranga, Kumar, Amit, Thakur, Rima
Format: Article
Language:English
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Summary:Stereoselective formation of glycosidic linkages has been the prime focus for contemporary carbohydrate chemistry. Herein, we report cyanomethyl (CNMe) ether as an efficient and effective participating orthogonal protecting group for the stereoselective synthesis of 1,2-trans-β-O-glycosides. The participating group facilitated good to high β-selective glycosylation with a broad range of electron-rich and electron-deficient glycosyl acceptors. Detailed experimental and theoretical studies reveal the involvement of CNMe ether in the formation of a six-membered imine-type cyclic intermediate for the observed stereoselectivity. Rapid incorporation and selective removal of the CNMe ether group in the presence of benzyl ether and isopropylidene acetal protection have also been reported here. The nitrile group provided an opportunity for the glycodiversification through further derivatizations.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.0c01249