Visible light activation enables the conversion of bench-stable sulfonates into valuable glycosides

Nature Synthesis (2022). DOI: 10.1038 / s44160-022-00162-w” width=”800″ height=”366″/>

A schematic diagram illustrating the design of a visible light-mediated system for mating several EVs with bench-stabilized heteroaryl sulfonate-derived glycosyl radicals. attributed to him: Nature synthesis (2022). DOI: 10.1038 / s44160-022-00162-w

Chemists at the National University of Singapore have developed a new strategy for generating therapeutically relevant C-glycosides and S-glycosides through a transition- and catalyst-free approach under visible-light illumination at ambient temperature. Their research appears in Nature synthesis.

Glycosides play an irreplaceable role in diverse physiological functions and are found in a variety of natural products and synthetic compounds. C-glycosides are an important class of glycosides, which consist of a sugar-containing unit linked to an organic moiety or other sugar-containing compound, through a carbon-carbon (CC) bond. They have a myriad of biological activities and are structurally diverse. One convenient method for constructing such products is the direct conjugation of a glycosyl precursor (the donor) with a carbon-based reagent.

However, the range of C-glycosides that can be accessed using the currently reported methods is very limited. This is due to the lack of practical glycosyl donors available to facilitate moderate CC conjugation. A general class of bench-stable glycosylation precursors that can be easily synthesized and isolated on a large scale, yet reactive enough to undergo rapid and steric selective cross-coupling at ambient conditions is highly desirable but elusive.

A research team led by Associate Professor Koh Ming Guo, from the Department of Chemistry at the National University of Singapore, has devised robust procedures for the fabrication of solid heterocyclic sulfate on a multigram scale. The team discovered that these bench-stable sulfonates are also redox-active. Using visible (blue) illumination and a Hantzsch ester-base compound, researchers are able to activate sulfonates to produce chemically reactive glycosyl radicals.

These radicals easily react with various electrical substances. Using this method, they are able to obtain a wider range of alkyl C, C-alkenyl, C-alkynyl, C-heteroaryl and S-linked glycosides in a highly efficient and selective manner. The researchers also used visible/ultraviolet absorption spectroscopy and radical clock studies to gain insight into the mechanism of these transitions.

Professor Koh said: “This metal-catalyzed and transition-free method effectively overcomes previous limitations in scale, scalability, and instability of glycosylation donors.”

“We expect this general class of glycosyl precursors and their newly discovered reaction under visible-light illumination to find significant benefit in various synthetic applications of carbohydrates, furthering efforts toward the discovery of novel sugar-based therapies and our understanding of biological processes,” the professor added. skylight.

The research team plans to work with companies to take advantage of these results for the synthesis of compounds derived from sugar.


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more information:
Quanquan Wang et al, Visible-light activation enables cross-conjugation of glycosylated sulfonates, Nature synthesis (2022). DOI: 10.1038 / s44160-022-00162-w

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