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Issue 9, 2013
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DFT studies on the mechanisms of palladium-catalyzed intramolecular arylation of a silyl C(sp3)–H bond

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Abstract

Detailed mechanisms of the intramolecular C(sp3)–C(sp2) bond formation via C(sp3)–H bond activation of a trimethylsilyl (TMS) substituent catalyzed by palladium(0) complexes have been investigated with the aid of density functional theory (DFT) calculations. The results reveal that the favorable catalytic cycle includes oxidative addition, ligand substitution, concerted metalation deprotonation (CMD) and reductive elimination steps. The CMD was found to be the rate-determining step with an overall free energy barrier of 26.4 kcal mol−1. For the analogous CMe3-substituted substrate, the C(sp3)–H bond activation of the CMe3 substituent was calculated to have a high free energy barrier of 29.9 kcal mol−1. Our calculation results show that during the deprotonation process of the TMS C(sp3)–H bond, the adjacent Si atom stabilizes the charge accumulated on the C(sp3)–H carbon and facilitates the C(sp3)–H bond activation due to the ability of Si to engage in Si–C hypervalent bonding.

Graphical abstract: DFT studies on the mechanisms of palladium-catalyzed intramolecular arylation of a silyl C(sp3)–H bond

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Publication details

The article was received on 17 May 2013, accepted on 25 Jun 2013 and first published on 26 Jun 2013


Article type: Paper
DOI: 10.1039/C3NJ00531C
New J. Chem., 2013,37, 2856-2861

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    DFT studies on the mechanisms of palladium-catalyzed intramolecular arylation of a silyl C(sp3)–H bond

    H. Xie, H. Zhang and Z. Lin, New J. Chem., 2013, 37, 2856
    DOI: 10.1039/C3NJ00531C

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