Wang Bo, Zhou Yu, Xu Niuniu, Xu Xiufang, Xu Xiaohua, Jin Zhong
State Key Laboratory and Institute of Elemento-organic Chemistry, College of Chemistry , Nankai University , Tianjin 300071 , China.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry , Nankai University , Tianjin 300071 , China.
Org Lett. 2019 Mar 15;21(6):1885-1889. doi: 10.1021/acs.orglett.9b00499. Epub 2019 Mar 1.
Pd(II)-catalyzed remote C-H olefination of aromatic tertiary amines was achieved with high meta selectivity. With the assistance of an elaborated template, C-H functionalization of unreactive aryl tertiary amines, hindered by the p-π conjugation between the lone-pair electrons of the nitrogen atom and the phenyl ring, was realized with high meta regioselectivity via a quaternary ammonium salt assembly. The results demonstrate that apart from the distance and geometry of the template, the conformation of the arene substrate also plays a crucial role in the templated-assisted remote C-H functionalization.
钯（II）催化的芳香叔胺远程C-H烯基化反应以高间位选择性实现。在精心设计的模板的辅助下，通过季铵盐组装，实现了未反应的芳基叔胺的C-H官能化，该反应受到氮原子孤对电子与苯环之间的p-π共轭的阻碍，并具有高间位区域选择性。结果表明，除了模板的距离和几何形状外，芳烃底物的构象在模板辅助的远程C-H官能化中也起着关键作用。
