A palladium-catalyzed regio- and diastereoselective diarylation of glycals and pseudoglycals, which is a kind of Heck-Suzuki arylation, is described. A wide range of arylboronic acids reacted under these conditions smoothly. Selectivity was C1-C2(α,α) in the case of glycals but C2-C3(β,β) for pseudoglycals. Quantum chemical analysis has been carried out to establish the reaction mechanism, which may involve Pd(II)/Pd(O). TEMPO plays a key role in the formation of diaryl glycoside due to its radical nature.

A highly stereoselective rapid C-glycosylation reaction has been developed between glycal and unactivated alkynes in the presence of coppertriflate and ascorbic acid at low catalyst loading and at room temperature. A wide variety of glycals and aryl acetylenes participate in the reaction smoothly. TfOH generated during the reduction of Cu(OTf)2 by ascorbic acid may be the active catalyst for the glycosylation.

Orthogonally protected monosaccharide building blocks have been prepared using TCT in a one-pot multicomponent transformation. The process involves successive steps of arylidene acetalation, esterification and regioselective reductive acetal cleavage. High regioselectivity, scope for using a broad range of substrates, functional group tolerance, mild reaction conditions, easy handling process and wide application range are a few advantages of the current process.

The palladium‐catalyzed stereoselective synthesis of 2,3‐deoxy‐C‐aryl glycosides was investigated. The strategy is based on the Pd‐catalyzed desulfitative Heck coupling of arylsulfonyl chlorides and glycals with good leaving groups. An attempt was made to establish the reaction mechanism, which may involve PdII/Pd0 interconversion under basic conditions.