Atom-Economic Synthesis of Unsymmetrical gem-Diarylmethylthio/Seleno Glycosides via Base Mediated C(O)–S/Se Bond Cleavage and Acyl Transfer Approach of Glycosylthio/Selenoacetates

• Published in: Journal of organic chemistry Vol. 88; no. 3; pp. 1695 - 1712
• Main Authors: Azeem, Zanjila, Mandal, Pintu Kumar
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.02.2023
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.2c02704

Herein, we invented the Cs2CO3-mediated atom economic method that streamlines the scission of the C­(O)–S/Se bond involving the in situ generation of an anomeric thiolate/selenolate anion, which reacted with p-QMs to yield novel unsymmetrical gem-diarylmethylthio/seleno glycosides while retaining the anomeric stereochemistry. Notably, the key features of this protocol involve unprecedented long-range acyl transfer (from S/Se to O), thus affording acylation of the final product which is not yet reported by classical methods. This straightforward protocol offers a mild, short reaction time, synthetically simple approach, and compatibility with 8 types of sugar along with phenylthio/benzylseleno esters.