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Ruthenium‐Catalyzed Highly Chemoselective Hydrogenation of Aldehydes

The use of a [(ethylenediamine)(dppe)Ru(OCOtBu)2] [dppe=1,2‐bis(diphenylphosphino)ethane] complex under base‐free conditions allowed highly efficient and selective hydrogenation of aldehydes in the presence of ketones in addition to olefins. Even in the case of highly sensitive 1,6‐ketoaldehydes, the desired ketoalcohols were obtained in high yields with 94–99 % overall selectivity at complete aldehyde conversion with a TON up to 30 000. The lack of requirement for strong basic co‐catalysts and polar protic solvents also allowed efficient and highly chemoselective reduction of aldehydes bearing other functional groups, such as epoxides, carboxylic acids, esters, amides, and nitriles emphasizing the potential synthetic utility of the catalyst.