Enantioselective Hydrogenation of Benzofurans with Water via Rh/Hf Cooperative Catalysts: Convenient Access to Chiral 2,3‐Dihydrobenzofurans

Comprehensive Summary The chiral 2,3‐dihydrobenzofuran (DHB) scaffold is a privileged motif in bioactive natural products and preclinical therapeutic candidates, yet practical enantioselective syntheses remain scarce. We report a chiral Rh/Hf/( S )‐DTBM‐SEGPHOS bimetallic catalytic system enabling asymmetric hydrogenation of benzofurans with hydrogen source, delivering diverse DHBs (37 examples) in excellent yields (up to 98%) and enantioselectivities (up to 99% ee ). Gram‐scale synthesis and deuterium labeling with D 2 O (8 examples) validate the method's scalability and utility in biological studies and drug design.