Ruthenium(II)-Catalyzed C@H Difluoromethylation of Ketoximes: Tuning the Regioselectivity from the meta to the para Position
Chunchen Yuan1,+, Lei Zhu2,+, Runsheng Zeng1, Yu Lan2,*(蓝宇), and Yingsheng Zhao1,*(赵应声)
1 Key Laboratory of Organic Synthesis of Jiangsu Province
College of Chemistry, Chemical Engineering, and Materials Science
Soochow University,Suzhou 215123 (P.R. China)
2 School of Chemistry and Chemical Engineering,Chongqing University,
Chongqing 40030 (P.R. China)
[+] These authors contributed equally.
Angew. Chem. Int. Ed.2018, 57, 1277--1281
A highlypara‐selective CAr−H difluoromethylation of ketoxime ethers under ruthenium catalysis has been developed. A wide variety of ketoxime ethers are compatible with the reaction, which leads to the correspondingpara‐difluoromethylated products in moderate to good yield. A mechanistic study clearly showed that chelation‐assisted cycloruthenation is the key factor in theparaselectivity of the difluoromethylation of ketoxime ethers. Density functional theory was used to gain a theoretical understanding of theparaselectivity.
链接:https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201711221