Visible-light irradiation of 4-p-methoxyphenyl-3-butenylthioglucoside donors in the presence of Umemoto's reagent and alcohol acceptors serves as a mild approach to O-glycosylation. Visible-light photocatalysts are not required for activation, and alkyl- and arylthioglycosides not bearing the p-methoxystyrene are inert to these conditions. Experimental and computational evidence for an intervening electron donor-acceptor complex, which is necessary for reactivity, is provided. Yields with primary, secondary, and tertiary alcohol acceptors range from moderate to high. Complete β-selectivity can be attained through neighboring-group participation.

The effect of tethering a thioether to a rhodium(II) paddlewheel complex are evaluated in Si–H insertion reactions. This study provides further evidence for the benefits of incorporating thioethers into the rhodium paddlewheel motif. When using a tethered complex, the in situ carbenoid formation and subsequent Si–H insertion are not impeded, yields are improved by up to 12 % at elevated temperatures, and selectivity for diazo compounds is greater when compared to non‐tethered catalysts. Computational modelling of the complexes is also presented in order to rationalize the results.

Dirhodium(II) paddlewheel complexes have high utility in diazo-mediated cyclopropanation reactions and ethyl diazoacetate is one of the most commonly used diazo compounds in this reaction. In this study, we report...