Pd(II)-catalyzed ortho trifluoromethylation of arenes and insights into the coordination mode of acidic amide directing groups.
A Pd(II)-catalyzed trifluoromethylation of ortho C-H bonds with an array of N-arylbenzamides derived from benzoic acids is reported. N-Methylformamide has been identified as a crucial promoter of C-CF(3) bond formation from the Pd center. X-ray characterization of the C-H insertion intermediate has revealed a rare coordination mode of acidic amides as directing groups and the origin of their capacity in directing C-H activation.
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Xing-Guo
XG
Zhang
Hui-Xiong
HX
Dai
Masayuki
M
Wasa
Jin-Quan
JQ
Yu
D001549:Benzamides / Q000737:chemistry*; D001565:Benzoates / Q000737:chemistry*; D002384:Catalysis; D005559:Formamides / Q000737:chemistry*; D054879:Halogenation; D008745:Methylation; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*
D001549:Benzamides; D001565:Benzoates; D005559:Formamides; D010165:Palladium; C037689:benzamide; C002950:methylformamide