Nickel-Catalyzed Asymmetric Reductive 1,4- and 1,5-Dicarbofunctionalization†

Abstract

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(sp³)- and C(sp²)-type carbo-moieties are respectively installed on the terminal and internal position with a newly formed olefinic unit in high E-selectivity.