Desulfitative C‐Arylation of Glycals by Using Benzenesulfonyl Chlorides

Abstract

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.

Stereocontrolled Synthesis of Highly Substituted trans α,β‐Unsaturated Ketones with Potent Anticancer Properties from Glycals

“…(Scheme b) . Related results reported by Mukherjee et al demonstrated the application of the Pd‐catalysed desulfitative coupling of sulfonyl chlorides in processes yielding the same type of products …”

“…[35] Related results reported by Mukherjee et al demonstrated the application of the Pd-catalysed desulfitative coupling of sulfonyl chlorides in processes yielding the same type of products. [30] The open chain trans alkenes are also possible outcomes of the glycal transformations as demonstrated by Ye et al in Hecktype reactions carried out with Ni-catalyst and boronic acids as the reactant (Scheme 1c). [29] An additional work describing formation of the open chain products in the reaction of glycals and terminal alkynes under metal-free conditions has been reported recently expanding further synthetic potential of these carbohydrate derivatives (Scheme 1d).…”

“…[21][22][23][24][25][26][27][28] Numerous variants of transition or other metals promoted reactions of glycals have been developed to allow easy access to C-glycosides which can be transformed into other useful molecules. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] Amongst the metal promoted processes, Pd-catalyzed Heck-type reactions of glycals have been studied the most extensively. Besides a typical Heck product created through the addition of organopalladium species followed by a Pd-hydride elimination, various other products can be also accessed either via in situ transformation or via an additional synthetic step.…”

“…In this regard, glycals are particularly interesting and they have been intensively studied in recent years . Numerous variants of transition or other metals promoted reactions of glycals have been developed to allow easy access to C‐glycosides which can be transformed into other useful molecules . Amongst the metal promoted processes, Pd‐catalyzed Heck‐type reactions of glycals have been studied the most extensively.…”

Halo-substituted benzenesulfonyls and benzenesulfinates: convenient sources of arenes in metal-catalyzed C–C bond formation reactions for the straightforward access to halo-substituted arenes

“…This method provides a straightforward access to the halo-substituted β-aryl ketones 79 in moderate to good yields, as they demonstrated the compatibility of this reaction with iodo-and bromo-functionalities on the benzenesulfinate. 76 Their strategy was based on use of OAc as leaving group. The use of 10 mol% PdCl 2 (PPh 3 ) 2 catalyst, Li 2 CO 3 base in dioxane at 140 °C was found to be the optimal conditions.…”