Study of Lewis acid accelerated palladium catalyzed CH activation

[Display omitted] •Amide and urea directed ortho-acylation and ortho-olefination on aromatic cores is accelerated by Lewis acidic additives.•Lewis acidic additives afford more electrophilic transition metal center, favoring CH activation.•The efficiency of several palladium(II) catalysts is raised.•...

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Bibliographic Details
Published inJournal of molecular catalysis. A, Chemical Vol. 426; pp. 444 - 450
Main Authors Tischler, Orsolya, Kovács, Szabolcs, Érsek, Gábor, Králl, Péter, Daru, János, Stirling, András, Novák, Zoltán
Format Journal Article
LanguageEnglish
Published Elsevier B.V 01.01.2017
Subjects
C[sbnd]H activation
DFT studies
Lewis acid
palladium
Lewis acid
CH activation
DFT studies
palladium
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Summary:[Display omitted] •Amide and urea directed ortho-acylation and ortho-olefination on aromatic cores is accelerated by Lewis acidic additives.•Lewis acidic additives afford more electrophilic transition metal center, favoring CH activation.•The efficiency of several palladium(II) catalysts is raised.•KIE experiments and calculations suggests a rate-determining CH activation step. Acceleration of palladium catalyzed CH activation by various Lewis Acids was demonstrated on the directed ortho-alkenylation and acylation of acetanilide and urea derivatives. The universality of this effect was investigated by the study of different palladium catalysts, directing groups in the aromatic substrates and versatile Lewis acids. Experiments were carried out to monitor the reactions and to compare the behavior and activity of different types of Lewis acids. Kinetic investigation revealed a rate determining CH activation step, and DFT studies were performed for the explanation of Lewis acid effect on CH activation.
ISSN:1381-1169
1873-314X
DOI:10.1016/j.molcata.2016.09.018