Stereoselective C ‐Aryl Glycosylation by Catalytic Cross‐Coupling of Heteroaryl Glycosyl Sulfones

作者：Quanquan Wang, Boon Chong Lee, NingXi Song, Ming Joo Koh · 发表于：Angewandte Chemie International Edition · 年份：2023 · DOI：10.1002/anie.202301081 · 被引用次数：81 · 研究领域：Carbohydrate Chemistry and Synthesis、Sulfur-Based Synthesis Techniques、Legume Nitrogen Fixing Symbiosis

Stereoselective C-glycosylation reactions are increasingly gaining attention in carbohydrate chemistry because they enable glycosyl precursors, readily accessible as anomeric mixtures, to converge to a single diastereomeric product. However, controlling the stereochemical outcome through transition-metal catalysis remains challenging, and methods that leverage bench-stable heteroaryl glycosyl sulfone donors to facilitate glycosylation are rare. Herein, we show two complementary nonprecious metal catalytic systems, based on iron or nickel, which are capable of promoting efficient C-C coupling between heteroaryl glycosyl sulfones and aromatic nucleophiles or electrophiles through distinct mechanisms and modes of activation. Diverse C-aryl glycosides were secured with excellent selectivity, scope, and functional-group compatibility, and reliable access to both α and β isomers was possible for key sugar residues.