Stereoselective β‐ <i>C</i> ‐aryl Glycosylation Through Ni‐Catalyzed Reductive Cross‐Coupling

In comparison to well‐documented methods for accessing α‐ C ‐aryl glycosides,the stereoselective synthesis ofβ‐anomers remains challenging, as less reliable routes to β‐functionalisation are established. Metal‐catalyzed cross‐coupling is known as one of the most straightforward methods to afford stereoselectively β‐ C ‐aryl glycosides, this strategy often requires the use of elaborated glycosyl donors or sensitive aryl metals along with the use of strict anhydrous and oxygen‐free conditions. Herein, we report a robust and stereoselective synthesis of β‐ C ‐aryl glycosides by Ni‐catalyzed reductive cross‐coupling using readily available and bench‐stable materials. This reaction couples glycosyl halides and aryl halides in the presence of an air‐stable Ni 0 pre‐catalyst and a mild reductant. The reaction exhibits excellent β‐stereoselectivity with a broad range of carbohydrates and aryl moieties. Mechanistic studies, supported by density functional theory calculations, were performed to provide a rationale for the observed β‐stereoselectivity.