A versatile iridium catalyst for aldehyde reduction in water.

Catalysis in water has attracted increasing attention over the last several years in response to calls for sustainable chemistry. Recently, we and other groups explored the asymmetric transfer hydrogenation (ATH) of ketones and imines in neat water with a range of catalysts and found that the reaction generally affords fast rates and good to excellent enantioselectivities. We also demonstrated that aldehydes can be reduced to alcohols under transfer hydrogenation (TH) conditions in water with an iridium catalyst in a fast, highly chemoselective, and productive manner. Herein, we disclose that the same catalyst works efficiently for the hydrogenation of aldehydes in water as well. Although TH and hydrogenation catalysis can share the same hydridic intermediate, when, for example, the latter activates H2 heterolytically, few catalysts are effective for both reactions. Very recently, during the course of this study, Noyori, Ohkuma, and co-workers reported that the Ru-TsDPEN (TsDPEN= (1R,2R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) catalyst, one of the best catalysts for the ATH of ketones and imines, can be applied to the hydrogenation of ketones in methanol under slightly acidic conditions. Our study started with the reduction of benzaldehyde as a model reaction using tosylated Ir catalysts 1–5 in neat water.

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