Assembly of C-Alkyl Glycosides by Pd/NBE-Catalyzed 1,2-Functionalization of Glycals

C-alkyl glycosides constitute essential structural motifs in bioactive natural products and pharmaceutical compounds; however, their efficient synthesis continues to present substantial challenges. Herein, we describe a Catellani-reaction-enabled approach that overcomes traditional synthetic limitations, facilitating the direct and regioselective assembly of C-alkyl glycosides from alkyl halides. Our results establish the efficacy of the Catellani reaction for C-alkyl glycoside synthesis from alkyl halide precursors. Notably, this protocol displays exceptional functional group tolerance across diverse substrates while maintaining perfect regiocontrol, representing a significant advancement in Catellani reaction applications for C-glycoside construction.