Cross-coupling reactions have developed into powerful approaches for carbon-carbon bond formation. In this work, a Ni-catalyzed migratory Suzuki-Miyaura cross-coupling featuring high benzylic or allylic selectivity has been developed. With this method, unactivated alkyl electrophiles and aryl or vinyl boronic acids can be efficiently transferred to diarylalkane or allylbenzene derivatives under mild conditions. Importantly, unactivated alkyl chlorides can also be successfully used as the coupling partners. To demonstrate the applicability of this method, we showcase that this strategy can serve as a platform for the synthesis of terminal, partially deuterium-labeled molecules from readily accessible starting materials. Experimental studies suggest that migratory cross-coupling products are generated from Ni(0/II) catalytic cycle. Theoretical calculations indicate that the chain-walking occurs at a neutral nickel complex rather than a cationic one. In addition, the original-site cross-coupling products can be obtained by alternating the ligand, wherein the formation of the products has been rationalized by a radical chain process. 1 1234567890():,; Reductive conditions Redox-neutral conditions Redox-neutral conditions Alkyl reagents Metal migration a Migratory cross-coupling of alkyl electrophiles Ni-catalyzed reductive migratory cross-coupling (Zhu and our group): Pd-catalyzed migratory suzuki-miyaura cross-coupling (Sigman): Ni-catalyzed migratory suzuki-miyaura cross-coupling (this work): b c d Fig. 1 Transition metal-catalyzed migratory cross-coupling. a Migratory cross-coupling of alkyl electrophiles. b Ni-catalyzed reductive migratory crosscoupling. c Pd-catalyzed migratory Suzuki-Miyaura cross-coupling. d The approach developed in this study. ARTICLE NATURE COMMUNICATIONS | https://doi.

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<div>Cross-electrophile coupling has been developed into a practical approach for the construction of carbon-</div><div>carbon bonds, wherein nickel catalysis has been widely employed. Mechanistically, a catalytic cycle involving</div><div>sequentially selective oxidative addition or radical chain process is proposed. Although the catalytic cycle of dual nickel metathesis has been discussed in several important works, none thinks this pathway is possible. In this manuscript, we present a thorough mechanistic study by a series of designed experiments toward the nickel-catalyzed migratory reductive cross-coupling. The results suggest that a catalytic cycle involving two organonickel(II) species metathesis as a key step, operates in this reaction. Moreover, we provide a discussion on the difference between the nickel-catalyzed migratory reductive cross-couplings and the classical ones. Additionally, based on the mechanistic finding, a new catalytic system has also been developed, which allows the use of electron-deficient aryl halides as starting materials, affording the migratory cross-coupling products efficiently.</div>

<div>Cross-electrophile coupling has been developed into a practical approach for the construction of carbon-</div><div>carbon bonds, wherein nickel catalysis has been widely employed. Mechanistically, a catalytic cycle involving</div><div>sequentially selective oxidative addition or radical chain process is proposed. Although the catalytic cycle of dual nickel metathesis has been discussed in several important works, none thinks this pathway is possible. In this manuscript, we present a thorough mechanistic study by a series of designed experiments toward the nickel-catalyzed migratory reductive cross-coupling. The results suggest that a catalytic cycle involving two organonickel(II) species metathesis as a key step, operates in this reaction. Moreover, we provide a discussion on the difference between the nickel-catalyzed migratory reductive cross-couplings and the classical ones. Additionally, based on the mechanistic finding, a new catalytic system has also been developed, which allows the use of electron-deficient aryl halides as starting materials, affording the migratory cross-coupling products efficiently.</div>