Carbohydrates play a vital role within living organisms, present on proteins and cells. A plethora of natural products contain glycosyl moieties, and several have exhibited biological activity. For decades, synthetic chemists have developed methods for functionalizing saccharide cores, but a majority are limited to S<sub>N</sub>2 displacements of halogenated starting material. Alternative radical approaches exist, as demonstrated by Inoue and coworkers, although limitations include telluride radical precursors and poor diastereoselectivity. To the best of our knowledge, there are currently no reports of direct arylation of saccharides via nickel catalysis. Therefore, we have optimized conditions for coupling DHP saccharides with aryl bromides under the mild, additive-free photoredox/nickel conditions. Through this process, non-classical C-arylated monosaccharides are accessed in one step using a cheap organophotocatalyst 4CzIPN and benchtop-stable Ni(II) precomplex. A majority of the 20+ aryl glycosides reported exhibit high diastereoselectivity (&gt;20:1) and NMR studies are used to elucidate the major diastereomer. In addition to high <i>dr</i>, the mild photoredox conditions allow the incorporation of highly functionalized aryl bromide partners found in the Merck informer plate.

Photoredox-mediated arylation of 1,4-dihydropyridine monosaccharides

256th National Meeting (2018)

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