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 2018-01, Vol.130 (5), p.1291-1295
Main Authors: Yuan, Chunchen, Zhu, Lei, Zeng, Runsheng, Lan, Yu, Zhao, Yingsheng
Format: Article
Language:English
Subjects:
C-H-Aktivierung
Catalysis
Chelation
Chemistry
Density functional theory
Difluormethylierung
Ethers
Ketoximether
Regioselectivity
Regioselektivität
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.# para‐Parade: Ein breites Spektrum von Ketoximethern konnte in einer para‐selektiven CAr‐H‐Difluormethylierung unter Rutheniumkatalyse eingesetzt werden. Mechanistische Studien und DFT‐Rechnungen zeigen klar, dass die chelatisierungsunterstützte Cycloruthenierung der Schlüsselfaktor für die para‐Selektivität ist.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201711221