Selective Pd-Catalyzed Oxidative Coupling of Anilides with Olefins through C−H Bond Activation at Room Temperature

• Published in: Journal of the American Chemical Society 2002-02, Vol.124 (8), p.1586-1587
• Main Authors: Boele, Maarten D. K, van Strijdonck, Gino P. F, de Vries, André H. M, Kamer, Paul C. J, de Vries, Johannes G, van Leeuwen, Piet W. N. M
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Noncondensed benzenic compounds; Organic chemistry; Preparations and properties
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0176907

Using a high-throughput experimentation approach we found a selective and mild Pd-catalyzed oxidative coupling reaction between anilide derivatives and acrylates that occurs through ortho C−H bond activation. The reaction is carried out in an acidic environment and occurs even at room temperature with use of a cheap oxidant (benzoquinone) in yields up to 91%. The benzoquinone possibly also functions as a ligand, stabilizing the catalyst. From the electronic dependence of the reaction and the observed kinetic isotope effect (k H/k D = 3) the key step of the catalytic cycle is believed to be electrophilic attack by a [PdOAc]+ complex on the π-system of the arene.