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The Anionic Pathway in the Nickel-Catalysed Cross-Coupling of Aryl Ethers.

ABSTRACT: The Ni-catalysed cross-coupling of aryl ethers is a powerful method to forge new C-C and C-heteroatom bonds. However, the inert C(sp² )-O bond means that a canonical mechanism that relies on the oxidative addition of the aryl ether to a Ni⁰ centre is thermodynamically and kinetically unfavourable, which suggests that alternative mechanisms may be involved. Here, we provide spectroscopic and structural insights into the anionic pathway, which relies on the formation of electron-rich hetero-bimetallic nickelates by adding organometallic nucleophiles to a Ni⁰ centre. Assessing the rich co-complexation chemistry between Ni(COD)₂ and PhLi has led to the structures and solution-state chemistry of a diverse family of catalytically competent lithium nickelates being unveiled. In addition, we demonstrate dramatic solvent and donor effects, which suggest that the cooperative activation of the aryl ether substrate by Ni⁰ -ate complexes plays a key role in the catalytic cycle.

SUBMITTER: Borys AM

PROVIDER: S-EPMC8596537 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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The Anionic Pathway in the Nickel-Catalysed Cross-Coupling of Aryl Ethers.

Borys Andryj M AM Hevia Eva E

Angewandte Chemie (International ed. in English) 20211019 46

The Ni-catalysed cross-coupling of aryl ethers is a powerful method to forge new C-C and C-heteroatom bonds. However, the inert C(sp<sup>2</sup> )-O bond means that a canonical mechanism that relies on the oxidative addition of the aryl ether to a Ni<sup>0</sup> centre is thermodynamically and kinetically unfavourable, which suggests that alternative mechanisms may be involved. Here, we provide spectroscopic and structural insights into the anionic pathway, which relies on the formation of elect ...[more]

PMID: 34469021

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Project description:The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this reaction will simplify the synthesis of pharmaceuticals, many of which are currently made with pre-formed organometallic reagents, and lead to the discovery of new multimetallic reactions.

Dataset Information

The Anionic Pathway in the Nickel-Catalysed Cross-Coupling of Aryl Ethers.

Publications

The Anionic Pathway in the Nickel-Catalysed Cross-Coupling of Aryl Ethers.

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