A Practical Transition Metal-Free Aryl-Aryl Coupling Method: Arynes as Key Intermediates

A Practical Transition Metal-Free Aryl-Aryl Coupling Method: Arynes as Key Intermediates. Frédéric R. Leroux, Laurence Bonnafoux, Christophe Heiss, Françoise Colobert, & Don Antoine Lanfranchi Adv. Synth. Catal., 349(17-18):2705–2713, December, 2007.

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Abstract Upon treatment of various aryllithium intermediates with 1,2-dibromobenzene or 1-bromo-2-iodobenzene, dissymmetrical ortho,ortho?-di-, tri- and even tetrasubstituted bromo- or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by ?-elimination of a lithium halide and, stabilization of the resulting 2-biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal-free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono- and diphosphine ligands.

@article{fredericr_leroux_practical_2007,
	title = {A {Practical} {Transition} {Metal}-{Free} {Aryl}-{Aryl} {Coupling} {Method}: {Arynes} as {Key} {Intermediates}},
	volume = {349},
	issn = {1615-4150},
	url = {https://doi.org/10.1002/adsc.200700211},
	doi = {10.1002/adsc.200700211},
	abstract = {Abstract Upon treatment of various aryllithium intermediates with 1,2-dibromobenzene or 1-bromo-2-iodobenzene, dissymmetrical ortho,ortho?-di-, tri- and even tetrasubstituted bromo- or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by ?-elimination of a lithium halide and, stabilization of the resulting 2-biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal-free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono- and diphosphine ligands.},
	number = {17-18},
	journal = {Adv. Synth. Catal.},
	author = {{Frédéric R. Leroux} and {Laurence Bonnafoux} and {Christophe Heiss} and {Françoise Colobert} and {Don Antoine Lanfranchi}},
	month = dec,
	year = {2007},
	keywords = {arynes, biaryls, CC coupling, halogen/metal exchange, phosphines},
	pages = {2705--2713},
}

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