The Implications of the Brønsted Acidic Properties of Crabtree-Type Catalysts in the Asymmetric Hydrogenation of Olefins.

Chiral iridium complexes derived from Crabtree's catalyst are highly useful in modern hydrogenations of olefins attributed to high reactivity, stereoselectivity, and stability. Despite that these precatalysts are pH neutral, the reaction mixtures turn acidic under hydrogenation conditions. This Perspective is devoted to the implications of the intrinsic Brønsted acidity of catalytic intermediates in asymmetric hydrogenation of olefins. Despite that the acidity has often been used only as a rationale for side-product formation, more recent methodologies have started to use this property advantageously. We hope that this Perspective serves as a stimulant for the development of such compelling and new asymmetric hydrogenations. The inherent scientific opportunities in utilizing or annihilating the generated Brønsted acid are enormous, and potential new innovations are outlined toward the end.