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Article Dans Une Revue Journal of the American Chemical Society Année : 2023

Shedding Light on the Hidden Roles of Lithium in the Nickel-Catalyzed Cross-Coupling of Aryl Ethers

Résumé

The Ni-catalyzed cross-coupling of aryl ethers is a powerful synthetic tool to transform widely available phenolderivatives into functionalized aromatic molecules. Recent theoretical and experimental mechanistic studies have identified the involvement of heterobimetallic nickelates as key intermediates that facilitate the challenging transformation under mild conditions, and often without the need for external ligands or additives. In this work, based on calculations performed at the DFT level and by comparison with spectroscopic and kinetic data, we investigate the mechanism of the Ni(COD)2 catalyzed cross-coupling of 2-methoxynaphthalene with PhLi, and assess the speciation of lithium nickelate intermediates. The crucial role of solvent on the reaction is explained and the multiple roles played by lithium are unveiled. Experimental studies have identified key lithium nickelate species which support and help evolve the calculated reaction mechanism, and ultimately complete the catalytic cycle. Based on this new mechanistic knowledge, a well-known experimental challenge of these transformations, the so-called "naphthalene problem" which restricts the use of electrophilic coupling partners to π-extended systems, can be addressed to enable the cross-coupling of unbiased aryl ethers under mild conditions.
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Dates et versions

hal-04285601 , version 1 (14-11-2023)

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Haosheng Liang, Andryj Borys, Eva Hevia, Marie-Eve Perrin, Pierre-Adrien Payard. Shedding Light on the Hidden Roles of Lithium in the Nickel-Catalyzed Cross-Coupling of Aryl Ethers. Journal of the American Chemical Society, 2023, 145 (36), pp.19989-19999. ⟨10.1021/jacs.3c06647⟩. ⟨hal-04285601⟩
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