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Stille coupling via C-N bond cleavage.

ABSTRACT: Cross-coupling is a fundamental reaction in the synthesis of functional molecules, and has been widely applied, for example, to phenols, anilines, alcohols, amines and their derivatives. Here we report the Ni-catalysed Stille cross-coupling reaction of quaternary ammonium salts via C-N bond cleavage. Aryl/alkyl-trimethylammonium salts [Ar/R-NMe₃]⁺ react smoothly with arylstannanes in 1:1 molar ratio in the presence of a catalytic amount of commercially available Ni(cod)₂ and imidazole ligand together with 3.0 equivalents of CsF, affording the corresponding biaryl with broad functional group compatibility. The reaction pathway, including C-N bond cleavage step, is proposed based on the experimental and computational findings, as well as isolation and single-crystal X-ray diffraction analysis of Ni-containing intermediates. This reaction should be widely applicable for transformation of amines/quaternary ammonium salts into multi-aromatics.

SUBMITTER: Wang DY

PROVIDER: S-EPMC5056441 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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Stille coupling via C-N bond cleavage.

Wang Dong-Yu DY Kawahata Masatoshi M Yang Ze-Kun ZK Miyamoto Kazunori K Komagawa Shinsuke S Yamaguchi Kentaro K Wang Chao C Uchiyama Masanobu M

Nature communications 20160930

Cross-coupling is a fundamental reaction in the synthesis of functional molecules, and has been widely applied, for example, to phenols, anilines, alcohols, amines and their derivatives. Here we report the Ni-catalysed Stille cross-coupling reaction of quaternary ammonium salts via C-N bond cleavage. Aryl/alkyl-trimethylammonium salts [Ar/R-NMe<sub>3</sub>]<sup>+</sup> react smoothly with arylstannanes in 1:1 molar ratio in the presence of a catalytic amount of commercially available Ni(cod)<sub ...[more]

PMID: 27686744

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