No abstract

No abstract

1,1-Diarylalkanes are important structural frameworks which are widespread in biologically active molecules. Herein, we report a reductive relay cross-coupling of alkyl bromides with aryl bromides by nickel catalysis with a simple nitrogen-containing ligand. This method selectively affords 1,1diarylalkane derivatives with good to excellent yields and regioselectivity.

A novel method to access 1,1-diarylalkanes from readily available, nonactivated alkyl bromides and aryl bromides via visible-light-driven nickel and iridium dual catalysis, wherein diisopropylamine ( PrNH) is used as the terminal stoichiometric reductant, is reported. Both primary and secondary alkyl bromides can be successfully transformed into the migratory benzylic arylation products with good selectivity. Additionally, this method showcases tolerance toward a wide array of functional groups and the presence of bases.

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.