Ligand‐Enabled Nickel‐Catalyzed Redox‐Relay Migratory Hydroarylation of Alkenes with Arylborons

Abstract

Aredox-relay migratory hydroarylation of isomeric mixtures of olefins with arylboronic acids catalyzedb yn ickel complexes bearing diamine ligands is described. Ar ange of structurally diverse 1,1-diarylalkanes,including those containing a1 ,1-diarylated quaternary carbon, were obtained in excellent yields and with high regioselectivity.P reliminary experimental evidence supports the proposed non-dissociated chainwalking of aryl-nickel(II)-hydride species along the alkyl chain of alkenes before selective reductive elimination at ab enzylic position. Ac atalyst loading as low as 0.5 mol % proved to be sufficient in large-scale synthesis while retaining high reactivity,h ighlighting the practical value of this transformation.[*] Y. He, Prof. S. Zhu Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Synergistic Ni/Cu catalyzed migratory arylsilylation of terminal olefins

“…The selectivity for the 1,2addition is likely due to the stability of the products by the conjugation effect of the aryl group. It is noteworthy that the yields can be further improved by addition of Ph 3 SiH and the corresponding aryl bromide (4a, 4e, 4f, 4ab), since the byproducts of the silyl-Heck reaction can also be converted to the corresponding arylsilylation products under these conditions [58]. However, no arylsilylation products were isolated in the reactions of branched or internal olefins (see Fig.…”