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Article
Stereoselective Synthesis of Nojirimycin α-C-Glycosides from a Bicyclic Acyliminium Intermediate: A Convenient Entry to N,C-Biantennary Glycomimetics
Author/s | Herrera González, Irene
González Cuesta, Manuel García Moreno, M. Isabel García Fernández, José Manuel Ortiz Mellet, Carmen |
Department | Universidad de Sevilla. Departamento de Química orgánica |
Publication Date | 2022 |
Deposit Date | 2022-07-11 |
Published in |
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Abstract | A simple and efficient method for the stereoselective synthesis of nojirimycin α-C-glycoside derivatives has been developed using a bicyclic carbamate-type sp2-iminosugar, whose preparation on a gram scale has been optimized, ... A simple and efficient method for the stereoselective synthesis of nojirimycin α-C-glycoside derivatives has been developed using a bicyclic carbamate-type sp2-iminosugar, whose preparation on a gram scale has been optimized, as the starting material. sp2-iminosugar O-glycosides or anomeric esters serve as excellent precursors of acyliminium cations, which can add nucleophiles, including C-nucleophiles. The stereochemical outcome of the reaction is governed by stereoelectronic effects, affording the target α-anomer with total stereoselectivity. Thus, the judicious combination of C-allylation, carbamate hydrolysis, cross-metathesis, and hydrogenation reactions provides a very convenient entry to iminosugar α-C-glycosides, which have been transformed into N,C-biantennary derivatives by reductive amination or thiourea-forming reactions. The thiourea adducts undergo intramolecular cyclization to bicyclic iminooxazolidine iminosugar α-C-glycosides upon acid treatment, broadening the opportunities for molecular diversity. A preliminary evaluation against a panel of commercial glycosidases validates the approach for finely tuning the inhibitory profile of glycomimetics. |
Funding agencies | Ministerio de Ciencia e Innovación (MICIN). España European Community (EC) Junta de Andalucía |
Project ID. | (Grant number P20_00166)
grant nos. PID2019-105858RB-I00 and RTI2018-097609-B-C21 10.13039/ 501100011033 |
Citation | Herrera González, I., González Cuesta, M., García Moreno, M.I., García Fernández, J.M. y Ortiz Mellet, C. (2022). Stereoselective Synthesis of Nojirimycin α-C-Glycosides from a Bicyclic Acyliminium Intermediate: A Convenient Entry to N,C-Biantennary Glycomimetics. ACS Omega, 7 (26), 22394-22405. |
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