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Site-Selective and Stereoselective C–H Alkylations of Carbohydrates via Combined Diarylborinic Acid and Photoredox Catalysis

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journal contribution
posted on 22.03.2019, 00:00 by Victoria Dimakos, Hsin Y. Su, Graham E. Garrett, Mark S. Taylor
Diphenylborinic acid serves as a cocatalyst for site- and stereoselective C–H alkylation reactions of carbohydrates under photoredox conditions using quinuclidine as the hydrogen atom transfer mediator. Products arising from selective abstraction of the equatorial hydrogens of cis-1,2-diol moieties, followed by C–C bond formation with net retention of configuration, are obtained. Computational modeling supports a mechanism involving formation of a tetracoordinate borinic ester, which accelerates hydrogen atom transfer with the quinuclidine-derived radical cation through polarity-matching and/or ion-pairing effects.