Oi Shuichi, Aizawa Emi, Ogino Yukako, Inoue Yoshio
Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan.
J Org Chem. 2005 Apr 15;70(8):3113-9. doi: 10.1021/jo050031i.
The ortho position of the aromatic ring in 2-aryloxazolines and 2-arylimidazolines is selectively arylated and alkenylated with organic halides in the presence of a ruthenium(II)-phosphine complex. In the case of unsubstituted and para-substituted phenyloxazolines, 1:2 coupled products were obtained preferentially, while 1:1 coupled products were obtained in the case of meta-substituted phenyloxazolines and N-acylarylimidazolines. The reaction is proposed to proceed via the generation of an organoruthenium intermediate, formed by oxidative addition of the organic halide, and ortho-ruthenation directed by the coordination of the 2-oxazolinyl or 2-imidazolinyl group to the ruthenium center.
在钌（II）-膦配合物存在下，2-芳基恶唑啉和2-芳基咪唑啉中芳环的邻位可与有机卤化物选择性地进行芳基化和烯基化反应。对于未取代和对位取代的苯基恶唑啉，优先得到1:2的偶联产物，而间位取代的苯基恶唑啉和N-酰基芳基咪唑啉则得到1:1的偶联产物。该反应被认为是通过生成有机钌中间体进行的，该中间体由有机卤化物的氧化加成形成，并由2-恶唑啉基或2-咪唑啉基与钌中心的配位导向邻位钌化。
