C‐aryl glycosyl compounds offer better in vivo stability relative to O‐ and N‐glycoside analogues. C‐aryl glycosides are extensively investigated as drug candidates and applied to chemical biology studies. Previously, C‐aryl glycosides were derived from lactones, glycals, glycosyl stannanes, and halides, via methods displaying various limitations with respect to the scope, functional‐group compatibility, and practicality. Challenges remain in the synthesis of C‐aryl nucleosides and 2‐deoxysugars from easily accessible carbohydrate precursors. Herein, we report a cross‐coupling method to prepare C‐aryl and heteroaryl glycosides, including nucleosides and 2‐deoxysugars, from glycosyl esters and bromoarenes. Activation of the carbohydrate substrates leverages dihydropyridine (DHP) as an activating group followed by decarboxylation to generate a glycosyl radical via C−O bond homolysis. This strategy represents a new means to activate alcohols as a cross‐coupling partner. The convenient preparation of glycosyl esters and their stability exemplifies the potential of this method in medicinal chemistry.
C-acyl furanosides are versatile synthetic precursors to a variety of natural products, nucleoside analogues, and pharmaceutical molecules. This report addresses the unmet challenge in preparing C-acyl furanosides by developing a...
The first example of an azidotrifluoromethoxylation of styrenes has been achieved by synergistic visible-light-mediated photoredox and silver catalysis. Trifluoromethyl arylsulfonate (TFMS) and the Zhdankin reagent were used as the trifluoromethoxylation reagent and the azide source, respectively. A good functional group tolerance and mild reaction conditions of this method are applicable to late-stage azidotrifluoromethoxylation of complex small molecules. Furthermore, the mechanistic investigations indicate the single-electron transfer involved in the reaction.
A novel palladium N-heterocyclic bis-carbene dicarboxylate ligand (Pd-NHDC-HL) was successfully synthesized. In addition, an Pd-NHDC-containing UiO-67 type MOF (UiO-67-Pd-NHDC) was prepared on the basis of a size-matched ligand mixture of biphenyl-4,4'-dicarboxylic acid/Pd-NHDC-HL (9/1) and ZrCl under solvothermal conditions. The obtained UiO-67-Pd-NHC MOF can be a highly heterogeneous catalyst to promote Heck cross-coupling and intermolecular benzyne-benzyne-alkene insertion reactions.
A catalytic ring-opening reaction of epoxides by nucleophilic trifluoromethoxylation of trifluoromethyl arylsulfonate has been developed based on the use of a cobalt catalyst. This reaction provides an efficient, simple route for directly construction of a wide range of vicinal trifluoromethoxyhydrins under mild conditions. In addition, this method can convert terminal epoxides into target products with good chemo-and regioselectivity.
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