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Issue 14, 2018
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A computational mechanistic study of Pd(II)-catalyzed γ-C(sp3)–H olefination/cyclization of amines: the roles of bicarbonate and ligand effect

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Abstract

The detailed mechanism of palladium-catalyzed γ-C(sp3)–H olefination/cyclization of triflyl-protected amines was investigated by density functional theory (DFT) calculations. The olefinated intermediate was initially formed in the first catalytic cycle involving ligand exchange, bicarbonate-assisted C(sp3)–H bond cleavage, alkene insertion and ‘reductive β-hydride elimination’. The following syn-addition and reductive elimination furnish the aza-Wacker product. The first step of reductive elimination is the rate-determining step. The mechanism unveils the important roles of bicarbonate: aiding the C–H activation and abstracting the β-proton in the second step of reductive elimination. The parallel bridging mode in the metal-olefin intermediate facilitates the syn-addition, explaining the experimentally observed stereoselectivity. The effect of the monodentate pyridine-based ligands is also discussed.

Graphical abstract: A computational mechanistic study of Pd(ii)-catalyzed γ-C(sp3)–H olefination/cyclization of amines: the roles of bicarbonate and ligand effect

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Publication details

The article was received on 02 Jan 2018, accepted on 10 Mar 2018 and first published on 12 Mar 2018


Article type: Paper
DOI: 10.1039/C8DT00015H
Citation: Dalton Trans., 2018,47, 4893-4901
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    A computational mechanistic study of Pd(II)-catalyzed γ-C(sp3)–H olefination/cyclization of amines: the roles of bicarbonate and ligand effect

    J. Liu, Y. Tian, X. Zhang, L. Wang and D. Chen, Dalton Trans., 2018, 47, 4893
    DOI: 10.1039/C8DT00015H

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