The hydrolytic stability of C-glycosides and their nuanced conformational properties compared to their O-glycoside parents have led to considerable interest in their applications as biomolecular probes and therapeutics, and by extension, their synthesis. Against this backdrop, several new synthetic methodologies have recently appeared, yet these approaches are generally not applicable to C1(sp³)-C(sp³) linked mimetics the vast majority of naturally occurring glycans. In this context, we have been developing a broad-based methodology that centers on the reaction of C-glycosyl crotylating agents with aldehydes, and elaboration of their products to methylene-linked, “exact” C-glycosides of biologically relevant glycans. The scope of this strategy will be illustrated by the use of C-glycosyl crotylboronates to access C-glycosides of α-D-Gal-(1→4)-D-Gal and α-D-Gal-(1→3)-D-Gal, which are ubiquitous subunits in higher order pyrano and furano glycan frameworks, including Galpα1,4Galpβ1,4Glcp (Gb3), Galpα1,3Galpβ1,4GlcNAcpα (α-Gal epitope), Galpα1,3Galfβ (G27_SH), Galpα1,3Galfβ1,3Manpα (G30_SH).

Jiwani Peters

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