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Issue 43, 2010
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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

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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

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Publication details

The article was received on 31 May 2010, accepted on 23 Jul 2010 and first published on 07 Oct 2010


Article type: Paper
DOI: 10.1039/C0DT00578A
Citation: Dalton Trans., 2010,39, 10528-10535

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    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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