Stereoselective Construction of Glycosides Enabled by Glycosyl/ Glycal Metal Species

Xiaomei Wu; Xin Yan; Deyun Qian

doi:10.1055/a-2502-7759

Synthesis, Table of Contents

Synthesis 2025; 57(12): 1893-1906
DOI: 10.1055/a-2502-7759

short review

Stereoselective Construction of Glycosides Enabled by Glycosyl/ Glycal Metal Species

Xiaomei Wu

^aKey Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; Yunnan Key Laboratory of Research and Development for Natural Products; School of Pharmacy, Yunnan University, Kunming 650500, P. R. of China

^bSchool of Chemical Science and Technology, Yunnan University, Kunming 650500, P. R. of China

,

Xin Yan

^aKey Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; Yunnan Key Laboratory of Research and Development for Natural Products; School of Pharmacy, Yunnan University, Kunming 650500, P. R. of China

^bSchool of Chemical Science and Technology, Yunnan University, Kunming 650500, P. R. of China

,

Deyun Qian ∗

^aKey Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; Yunnan Key Laboratory of Research and Development for Natural Products; School of Pharmacy, Yunnan University, Kunming 650500, P. R. of China

^bSchool of Chemical Science and Technology, Yunnan University, Kunming 650500, P. R. of China

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Abstract

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Abstract

Glycosyl/glycal metal functionalization has emerged as an efficient protocol for the construction of glycosides. Benefitting from the rapid development of organometallic chemistry and transition-metal-catalyzed cross-coupling reactions, glycosyl-metal-mediated glycosylation has significantly expanded the space for glycoside synthesis recently. In this short review, we underscore the representative progress in this area, categorizing the advancements by the type of glycosyl/glycal metal species. The reaction mechanism, stereochemical control, synthetic utility, and unmet challenges are also discussed.

1 Introduction

2 Glycosyl/Glycal Lithium-Based Glycosylations

2.1 Preparation of Glycosyl/Glycal Lithium Reagents

2.2 Glycosylation with Glycosyl/Glycal Lithiums

3 Glycosyl/Glycal Stannane-Based Glycosylations

3.1 Preparation of Glycosyl/Glycal Stannane Reagents

3.2 Glycosylation with Glycosyl/Glycal Stannanes

4 Glycosyl/Glycal Boron-Based Glycosylations

4.1 Preparation of Glycosyl/Glycal Boron Compounds

4.2 Glycosylation with Glycosyl/Glycal Boron Compounds

5 Glycosylations Enabled by in situ Formed Glycosyl-Metal Intermediates

5.1 Hydrofunctionalization of Glycals

5.2 Functionalization/Glycosylation of Glycals

6 Conclusion and Outlook

Key words

glycosides - stereoselective glycosylation - glycosyl-metal species - cross-coupling - functionalization - carbohydrate chemistry

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References

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