Ruthenium(II)‐Catalyzed C−H Difluoromethylation of Ketoximes: Tuning the Regioselectivity from the meta to the para Position

A highly para‐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 corresponding para‐difluoromethylated products in moderate to good yield. A mechanistic study clea...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-01, Vol.57 (5), p.1277-1281
Main Authors: Yuan, Chunchen, Zhu, Lei, Zeng, Runsheng, Lan, Yu, Zhao, Yingsheng
Format: Article
Language:English
Subjects:
Catalysis
Chelation
C−H activation
Density functional theory
difluoromethylation
Ethers
ketoxime ethers
Regioselectivity
Ruthenium
Ruthenium compounds
Selectivity
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Summary:A highly para‐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 corresponding para‐difluoromethylated products in moderate to good yield. A mechanistic study clearly showed that chelation‐assisted cycloruthenation is the key factor in the para selectivity of the difluoromethylation of ketoxime ethers. Density functional theory was used to gain a theoretical understanding of the para selectivity.# Take the para chute: A variety of ketoxime ethers are suitable substrates for a highly para‐selective CAr−H difluoromethylation reaction under ruthenium catalysis. Mechanistic studies in combination with DFT calculations clearly show that chelation‐assisted cycloruthenation is the key factor for the para selectivity.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201711221