Organometallic Synthesis and Catalysis Group, Chemical Engineering, Division, CSIR-National Chemical Laboratory (CSIR-NCL), Dr. Homi Bhabha Road, Pune, 411 008, Maharashtra, India), Home page.
ChemSusChem. 2017 May 22;10(10):2242-2248. doi: 10.1002/cssc.201700321. Epub 2017 Apr 18.
An efficient solvent-free nickel-catalyzed method for C-H bond arylation of arenes and indoles has been developed, which proceeds expeditiously through chelation assistance. The reaction is highly selective for mono-arylation and tolerates sensitive and structurally diverse functionalities, such as halides, ethers, amines, indole, pyrrole and carbazole. This reaction represents the first example of a nickel-catalyzed C-H arylation by monochelate assistance and symbolizes a rare precedent in solvent-free C-H arylation. Mechanistic investigations by various controlled reactions, kinetic studies, and deuterium labeling experiments suggest that the arylation follows a single electron transfer (SET) pathway involving the turnover-limiting C-H nickelation process.
已开发出一种高效的无溶剂镍催化芳基和吲哚 C-H 键芳基化方法，该方法通过螯合辅助作用迅速进行。该反应对单芳基化具有高选择性，并能耐受敏感且结构多样的官能团，如卤素、醚、胺、吲哚、吡咯和咔唑。该反应代表了首例单螯合辅助的镍催化 C-H 芳基化反应，也是无溶剂 C-H 芳基化中罕见的先例。通过各种对照反应、动力学研究和氘标记实验进行的机理研究表明，芳基化遵循涉及周转限制的 C-H 镍化过程的单电子转移 (SET) 途径。
