Nickel‐Catalyzed Asymmetric Reductive 1,4‐ and 1,5‐Dicarbofunctionalization^†

Comprehensive Summary Herein, we present the first examples of asymmetric reductive 1,4‐dicarbofunctionalization of 1,3‐dienes and 1,5‐dicarbofunctionalization of vinylcyclopropanes, which proceed under the catalysis of a chiral nickel/bis‐imidazoline complex using alkyl halides and aryl iodides or alkenyl bromides as the electrophilic coupling partners. In these highly enantioselective transformations operating in a radical relay mechanism, the C(sp 3 )‐ and C(sp 2 )‐type carbo‐moieties are respectively installed on the terminal and internal position with a newly formed olefinic unit in high E ‐selectivity.