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As a development of traditional vinylogous Michael addition reactions, catalytic enantioselective γ‐functionalization of α,α‐dicyanoolefins possesses a remarkable advantage in carboxylic derivatives synthesis and has emerged as a powerful tool for the preparation of high value chemicals. In another hand, the development of versatile and highly efficient catalyst is quite critical for such asymmetric transformations. Herein, a newly developed chiral‐at‐metal rhodium (III) complex catalyzed enantioselective vinylogous Michael addition of α,α‐dicyanoolefins with α,β‐unsaturated 2‐acyl imidazoles has been realized, delivering the corresponding adducts in 68−89 % yields with up to 95 % enantioselectivity. The reaction can be conducted on a gram‐scale using a low catalyst loading (0.5 mol %) without impacting its efficiency.

The synthesis of carboxylic acids from low-value materials such as alkenes using CO 2 as a C 1 -building block remains a real challenge for synthetic chemists from both reactivity and selectivity perspectives. Electrochemical carboxylations have been examined but they remain limited, still suffering from a crucial lack of selectivity. Herein we report a catalytic protocol based on an electrogenerated Sm(II) catalyst as a powerful CO 2 reductant, able to perform exclusively anti-Markovnikov hydrocarboxylation of alkenes. This electrochemical approach overcomes several current limitations and allows direct β-hydrocarboxylation of styrene derivatives, in a regioselective manner.