C‐Aryl Glycosylation via Interrupted Pummerer Rearrangement^†

Abstract

Comprehensive SummaryC‐aryl glycosides are an important kind of carbohydrate derivatives for drug discovery, due to their distinctive attributes of resistance to hydrolysis from enzymes. Herein, C‐aryl glycosylation was established for the synthesis of 2‐sulfur C‐aryl glycals and 1,2‐dihydrobenzofuran‐fused C‐aryl glycosides via interrupted Pummerer process, featured with sulfonium‐tethered [3,3]‐sigmatropic rearrangement between sulfoxide glycals and phenols. This protocol offers a broad substrate scope with diverse glycosyl and phenols. Dapagliflozin, Empagliflozin, and Ipragliflozin analogs were straightforward achieved, respectively.

SO2F2‐Mediated Thioesterification of Carboxylic Acids with Thiols

“…Considering the great attention thioglycosides have aroused in pharmaceutical science, [37,38] we initiated our study employing 4-methylbenzoic acid 1 b (0.1 mmol, 1.0 equiv.) and 2,3,4,6tetra-O-acetyl-1-thio-β-D-glucopyranose 2 a (0.2 mmol, 2.0 equiv.)…”