Nickel-Catalyzed Homocoupling of Aryl Ethers with Magnesium Anthracene Reductant

Abstract

Nickel-catalyzed reductive homocoupling of aryl ethers has been achieved with Mg(anthracene)(thf)₃ as a readily available low-cost reductant. DFT calculations provided a rationale for the specific efficiency of the diorganomagnesium-type two-electron reducing agent. The calculations show that the dianionic anthracene-9,10-diyl ligand reduces the two aryl ether substrates, resulting in the homocoupling reaction through supply of electrons to the Ni-Mg bimetallic system to form organomagnesium nickel(0)-ate complexes, which cause two sequential C–O bond cleavage reactions. The calculations also showed cooperative actions of Lewis acidic magnesium atoms and electron-rich nickel atoms in the C–O cleavage reactions.

Key words

homocoupling - C–O bond activation - nickel catalyst - magnesium anthracene - DFT calculation

Publication History

Received: 24 April 2021

Accepted after revision: 17 May 2021

Accepted Manuscript online:
17 May 2021

Article published online:
15 June 2021

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