Palladium(II)-assisted Activation of Thioglycosides

Overview

Journal Org Biomol Chem

Publisher Royal Society of Chemistry

Specialties Biochemistry
Chemistry

Date 2021 Feb 18

PMID 33599667

Citations 5

Authors

Samira Escopy

Yashapal Singh

Alexei V Demchenko

Affiliations

Soon will be listed here.

Abstract

Described herein is the first example of glycosidation of thioglycosides in the presence of palladium(ii) bromide. While the activation with PdBr2 alone was proven feasible, higher yields and cleaner reactions were achieved when these glycosylations were performed in the presence of propargyl bromide as an additive. Preliminary mechanistic studies suggest that propargyl bromide assists the reaction by creating an ionizing complex, which accelerates the leaving group departure. A variety of thioglycoside donors in reactions with different glycosyl acceptors were investigated to determine the initial scope of this new reaction. Selective and chemoselective activation of thioglycosides over other leaving groups has also been explored.

Citing Articles

Ferric Chloride Promoted Glycosidation of Alkyl Thioglycosides.

Ridgway L, Das A, Shadrick M, Demchenko A Molecules. 2024; 29(20).

PMID: 39459213 PMC: 11510396. DOI: 10.3390/molecules29204845.

Direct Synthesis of Glycosyl Chlorides from Thioglycosides.

Hoard D, Sutar Y, Demchenko A J Org Chem. 2024; 89(10):6865-6876.

PMID: 38669055 PMC: 11555473. DOI: 10.1021/acs.joc.4c00244.

Expedient Synthesis of Superarmed Glycosyl Donors via Oxidative Thioglycosidation of Glycals.

Forsythe N, Mize E, Kashiwagi G, Demchenko A Synthesis (Stuttg). 2024; 56(7):1147-1156.

PMID: 38655286 PMC: 11034933. DOI: 10.1055/a-2183-0175.

Activation of Thioglycosides with Copper(II) Bromide.

Pooladian F, Escopy S, Demchenko A Molecules. 2022; 27(21).

PMID: 36364179 PMC: 9654402. DOI: 10.3390/molecules27217354.

HPLC-Based Automated Synthesis of Glycans in Solution.

Escopy S, Singh Y, Stine K, Demchenko A Chemistry. 2022; 28(39):e202201180.

PMID: 35513346 PMC: 9403992. DOI: 10.1002/chem.202201180.

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