Gram-scale synthesis of carboxylic acids via catalytic acceptorless dehydrogenative coupling of alcohols and hydroxides at an ultralow Ru loading

Acceptorless dehydrogenative coupling (ADC) of alcohols and water/hydroxides is an emergent and graceful approach to produce carboxylic acids. Therefore, it is of high demand to develop active and practical catalysts/catalytic systems for this attractive transformation. Herein, we designed and fabricated a series of cyclometallated N -heterocyclic carbene-Ru (NHC-Ru) complexes via ligand tuning of [Ru-1] , the superior complex in our previous work. Gratifyingly, gram-scale synthesis of carboxylic acids was efficiently enabled at an ultralow Ru loading (62.5 ppm) in open air. Moreover, effects of distinct ancillary NHC ligands and other parameters on this catalytic process were thoroughly studied, while further systematic studies were carried out to provide rationales for the activity trend of [Ru-1] - [Ru-7] . Finally, determination of quantitative green metrics illustrated that the present work exhibited superiority over representative literature reports. Hopefully, this study could provide valuable input for researchers who are engaging in metal-catalyzed ADC reactions. • Cyclometallated NHC-Ru complexes were made for acceptorless dehydrogenative coupling (ADC). • Gram-scale synthesis of carboxylic acids was efficiently enabled in the open air. • Ultralow Ru loading of 62.5 ppm was applied for ADC. • Effects of distinct ancillary NHC ligands and other process parameters were thoroughly studied. • Quantitative green metrics illustrate that the present work exhibit superiority over reported literature.