Selective Pd-catalyzed oxidative coupling of anilides with olefins through C-H bond activation at room temperature

Maarten D K Boele; Gino P F van Strijdonck; André H M de Vries; Paul C J Kamer; Johannes G de Vries; Piet W N M van Leeuwen

doi:10.1021/ja0176907

Selective Pd-catalyzed oxidative coupling of anilides with olefins through C-H bond activation at room temperature

J Am Chem Soc. 2002 Feb 27;124(8):1586-7. doi: 10.1021/ja0176907.

Authors

Maarten D K Boele¹, Gino P F van Strijdonck, André H M de Vries, Paul C J Kamer, Johannes G de Vries, Piet W N M van Leeuwen

Affiliation

¹ Institute of Molecular Chemistry, Faculty of Science, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands.

PMID: 11853427
DOI: 10.1021/ja0176907

Abstract

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 (kH/kD = 3) the key step of the catalytic cycle is believed to be electrophilic attack by a [PdOAc]+ complex on the pi-system of the arene.