Issue 43, 2010

DFT study of the mechanism of benzocyclobutene formation by palladium-catalysed C(sp3)–H activation: role of the nature of the base and the phosphine

Abstract

DFT(B3PW91) calculations of the mechanism of the intramolecular C(sp3)–H arylation of 2-bromo-tert-butylbenzene to form benzocyclobutene catalysed by Pd(PR3) (R = Me, tBu) and a base (acetate, bicarbonate, carbonate) show that the preferred mechanism is highly dependent on the nature of the phosphine and the base used in the calculations. With the experimental reagents (PtBu3 and carbonate) the rate-determining step is C–H activation with the base coordinated trans to the C–H bond. An agostic interaction of a geminal C–H bond with respect to the bond to be cleaved induces a lowering of the activation barrier.

Graphical abstract: DFT study of the mechanism of benzocyclobutene formation by palladium-catalysed C(sp3)–H activation: role of the nature of the base and the phosphine

Article information

Article type
Paper
Submitted
31 May 2010
Accepted
23 Jul 2010
First published
07 Oct 2010

Dalton Trans., 2010,39, 10528-10535

DFT study of the mechanism of benzocyclobutene formation by palladium-catalysed C(sp3)–H activation: role of the nature of the base and the phosphine

C. E. Kefalidis, O. Baudoin and E. Clot, Dalton Trans., 2010, 39, 10528 DOI: 10.1039/C0DT00578A

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