Understanding the mechanism and origins of stereoconvergence in nickel-catalyzed hydroarylation of 1,3-dienes with aryl boronates

Abstract

Nickel-catalyzed stereoselective hydroarylation is one of the most efficient methods to access functionalized arenes. Herein, computational studies have been applied to reveal the mechanism and origins of ligand-controlled enantioselectivity of Ni-catalyzed hydroarylation of 1,3-dienes using ethanol as the hydrogen source. DFT calculations show that the hydroarylation of (E)-diene takes place via concerted hydronickelation aided by boronate leading to an alkylnickel(II) intermediate, which further undergoes transmetallation and C–C reductive elimination to deliver the final chiral alkylarene. The hydronickelation is found to be the rate-determining step and is irreversible. The enantioselectivity is dominated by the transmetallation step, in which the ligand–substrate interactions are analyzed to unveil the source of stereocontrol. Besides, mechanistic studies demonstrate that the (Z)-diene initially reacts to offer a (S)-Z-alkyl-Ni(II) species, which preferably undergoes facile isomerization via σ–π–σ–π–σ interconversion to the (R)-E-alkyl-Ni(II) complex rather than the transmetallation step, thus ultimately generating the same (R)-alkylarene product as (E)-diene. Overall, the mechanistic understanding will be useful for the further advancement of asymmetric hydroarylation of dienes.