Site-Selective O-Arylation of Carbohydrate Derivatives through Nickel-Photoredox Catalysis

Site-selective O-arylations of glycoside-derived diols have been achieved by couplings with bromoarenes upon irradiation with blue LEDs in the presence of an iridium photocatalyst and a nickel complex. The use of hexamethylenetetramine (hexamine) in place of quinuclidine, along with the application of a methoxy-substituted 2,2 '-bipyridine ligand, provided improvements in yield for this relatively challenging substrate class. Selective arylation took place at the less sterically hindered OH group, as determined by the substitution pattern and configuration of the glycoside substrate. Percent buried volume calculations were used to quantify the relative levels of steric hindrance at the two reactive sites.