Convenient Synthesis of β‐<i>C</i>‐Acyl Glycosides and its Application in the Synthesis of Scleropentaside A, Scleropentaside B and the Derivatives of Dapagliflozin

C-Glycosides are a common feature in numerous bioactive natural compounds and play a crucial role as mimics of O/N-glycosides. Our process for synthesizing β-C-acyl glycosides involves a reductive cross-coupling of protected glycosyl bromides with the corresponding carboxylic acid, followed by base-assisted deprotection and isomerization. This method is compatible with diverse glycosyl donors, including disaccharides. Consequently, we achieved the total synthesis of the natural products scleropentaside A and scleropentaside B with exceptional efficiency. These β-C-acyl glycosides can be readily transformed into novel forms of C-glycosides capable of disrupting signaling pathways linked to various pathological conditions, such as diabetes.