Research Abstract


Stille coupling via C–N bond cleavage

2016年9月30日 Nature Communications 7 : 12937 doi: 10.1038/ncomms12937



Dong-Yu Wang, Masatoshi Kawahata, Ze-Kun Yang, Kazunori Miyamoto, Shinsuke Komagawa, Kentaro Yamaguchi, Chao Wang and Masanobu Uchiyama

Corresponding Authors

王 超
東京大学大学院 薬学系研究科

内山 真伸
東京大学大学院 薬学系研究科

山口 健太郎
徳島文理大学 香川薬学部

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.