Pd‐Catalyzed Ortho‐Directed C—H Glycosylation of Arenes Using N‐linked Bidentate Auxiliaries

Abstract

Main observation and conclusion A set of Pd‐catalyzed ortho‐directed C—H glycosylation reactions with glycosyl chloride donors using various N‐linked bidentate auxiliaries has been developed for synthesis of C‐aryl glycosides. A broad range of pyranose and furanose moieties can be installed on the ortho position of arylamine, carbazole, indole and benzylamine type substrates in high yield and with high regio‐ and diastereoselectivity. These auxiliaries can be readily installed and removed under relatively mild conditions.

Recent Advances and Strategies towards Synthesis of Indolyl and Tryptophan‐C‐Glycoside Scaffolds

“…The palladium-catalyzed ortho-directed C(sp2)À H functionalization was applied to arenes/heteroarenes with glycosyl chloride donors and auxiliary groups (Scheme 18). The catalytic cycle initiated with the complex formation and CÀ H palladation of substrate I to generate PdII palladacycle Further, Gong Chen's research group [63] explained the N-linked bidentate auxiliaries for CÀ H glycosylation of arenes. Different auxiliaries such as urea-linked and amide-linked on carbazole, benzylamine, indole, and arylamine lead to ortho-directed CÀ H glycosylation of pyranose and furanose moieties via using metal Pd as catalyst (Scheme 19).…”

Palladium-catalyzed C–H glycosylation and retro Diels–Alder tandem reaction via structurally modified norbornadienes (smNBDs)

“…[28][29][30][31][32][33][34][35] and the most efficient is Pd-catalyzed ortho-directed C-H glycosylation reactions to construct 2-indolyl-C-glycoside skeleton by using of glycosyl chloride donors. 36 (Scheme 1b) However, the construction of 4-indole-C-glycosides has not been reported. Therefore, the development of an efficient C-H glycosylation reactions to construct of 4-glycosylindole skeleton has important application value.…”

Stereoselective Synthesis of Indolyl-C-glycosides Enabled by Sequential Aminopalladation and Heck Glycosylation of 2-Alkynylanilines with Glycals

“…Recently, palladium catalysts have played a vital role in C–H glycosylation in the stereoselective synthesis of indolyl- C -glycosides. For instance (Scheme b), an elegant stereoselective C–H glycosylation of indoles enabled by palladium-catalyzed directed C–H bond activation has been independently reported by the groups of Chen, He, and Liu and Liu and Liang . However, these works rely on the use of strongly coordinating directing groups, which require additional steps for their installation and removal.…”