Yi Jun, Yang Li, Xia Chungu, Li Fuwei
†State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, People's Republic of China.
‡University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China.
J Org Chem. 2015 Jun 19;80(12):6213-21. doi: 10.1021/acs.joc.5b00669. Epub 2015 May 29.
An efficient nickel catalyst system for the direct ortho C-H alkynylation of the amides has been successfully developed with the directing assistance of 8-aminoquinoline. It was found that the flexible bis(2-dimethylaminoethyl) ether (BDMAE) ligand was critical to achieve the optimized reactivity. This protocol showed good tolerance toward not only a wide range of (hetero)aryl amides but also the rarely studied α,β-unsaturated alkenyl amide. The directing amide group could be easily transformed to aldehyde or ester in high yields. Meanwhile, the removable TIPS substituent on the resultant aryl/alkenyl alkynes could be further converted to an aryl moiety through a Sila-Sonogashira coupling reaction. This Ni-catalyzed alkynylation procedure provides an alternative approach to construct a C(sp(2))-C(sp) bond.
在8-氨基喹啉的导向辅助下，已成功开发出一种用于酰胺直接邻位C-H炔基化的高效镍催化剂体系。研究发现，柔性双（2-二甲基氨基乙基）醚（BDMAE）配体对于实现优化的反应活性至关重要。该方法不仅对多种（杂）芳基酰胺表现出良好的耐受性，而且对很少研究的α，β-不饱和烯基酰胺也具有良好耐受性。导向酰胺基团可以很容易地高产率转化为醛或酯。同时，所得芳基/烯基炔烃上的可去除三异丙基硅基（TIPS）取代基可通过硅基- Sonogashira偶联反应进一步转化为芳基部分。这种镍催化的炔基化过程为构建C（sp(2)）-C（sp）键提供了一种替代方法。
