Regio- and enantioselective remote hydroarylation using a ligand-relay strategy

The design of a single complicated chiral ligand to well-promote each step of an asymmetric cascade reaction is sometimes a formidable challenge in transition metal catalysis. In this work, a highly regio- and enantioselective Ni-catalysed migratory hydroarylation relay process has been achieved with the combination of two simple ligands, one which accomplishes chain-walking and the other causing asymmetric arylation. This formal asymmetric C(sp(3))-H arylation provides direct access to a wide range of structurally diverse chiral 1,1-diarylalkanes, a structural unit found in a number of bioactive molecules. The value of this strategy was further demonstrated by the Ni-catalysed migratory asymmetric 1,3-arylboration. Migratory alkene isomerizations and cross-coupling reactions are both possible under nickel catalysis, but usually require different conditions. Here the authors show a combined protocol to isomerize a double bond and then, via an in-situ exchange of ligands, perform an enantioselective C(sp2)-C(sp3) cross-coupling.

Automated summary

In this work, a highly regio- and enantioselective Ni-catalysed migratory hydroarylation relay process has been achieved with the combination of two simple ligands, providing direct access to a wide range of structurally diverse chiral 1,1-diarylalkanes. The value of this strategy was further demonstrated by the Ni-catalysed migratory asymmetric 1,3-arylboration.