Palladium‐Catalyzed Stereoselective C‐Glycosylation of Glycals with Sodium Arylsulfinates

Abstract

An efficient glycosylation method to synthesize 2-deoxy-Caryl glycosides was developed. This C-glycosylation strategy is based on a palladium-catalyzed desulfitative Ferrier-type coupling reaction of glycals and sodium arylsulfinates. A [a]General Experimental Procedure: Glycal (0.15 mmol), sodium arylsulfinate (0.6 mmol), PdCl 2 (0.015 mmol), CuCl 2 (0.15 mmol), and LiCl (0.15 mmol) were added to a 25 mL Schlenk tube. MeCN (3 mL) was then added by syringe. The tube was sealed with a rubber stopper and equipped with a balloon. The mixture was heated to 75°C (external temperature) for 8-12 h. The mixture was cooled to room temperature and filtered. The filtered cake was rinsed with EtOAc. The filtrate was concentrated and purified by column chromatography on silica gel (EtOAc/hexanes) to give the desired product.

Advances in Pd-catalyzed C–C bond formation in carbohydrates and their applications in the synthesis of natural products and medicinally relevant molecules

“…This method is based on a Pd-catalyzed desulfitative Ferrier-type coupling of glycals (20g) and sodium arylsulfinates (123) to produce aryl- C- glycosides (124a–e) with 100% α-selectivity ( Scheme 34 ). 76 …”

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

“…Two months later, Ma, Liu et al described the same reaction using sodium benzenesulfinates as aryl sources (Scheme 45, b). 77 CuCl 2 was used as the oxidant and the reaction was performed under air atmosphere. The Pd-catalyzed reaction of halo-substituted benzenesulfonyl chlorides with enones was investigated by our group (Scheme 48).…”

Glycosylation via Transition‐Metal Catalysis: Challenges and Opportunities

“…In 2013, Liu and co‐workers described the synthesis of α‐ C ‐aryl glycosides, such as 210 and 214 – 217 in good to excellent yields from 23 and various aryl hydrazines . Recently, Liu and co‐workers also disclosed the synthesis of α‐ C ‐aryl glycosides, such as 210 , 213 , and 215 – 216 in good yields from 23 and various arylsulfinates . Notably, under this condition the C ‐aryl glycoside 213 bearing chlorine at para ‐position was obtained in higher yield than the Maddaford's method.…”