Photoinduced Excited‐State Pd(0)‐Catalyzed Stereoselective <i>C</i>‐Glycosylation of 1‐Bromosugar with Quinoxalin‐2(1<i>H</i>)‐one

Herein, an α-selective synthesis of C-glycoside with 1-bromosugars and quinoxalin-2(1H)-ones is reported, leveraging visible light-mediated excited-state palladium catalysis. This process involves the generation of glycosyl radicals from easily accessible 1-bromosugar precursors, which can capture quinoxalinone under photoinduced Pd(0) catalysis. The reaction operates under mild conditions, offering excellent axial selectivity with a diverse array of substrates. This methodology will provide a valuable platform for constructing potent biologically active C-glycosides.