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Issue 23, 2018
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Dehydrogenative coupling of 4-substituted pyridines mediated by a zirconium(II) synthon: reaction pathways and dead ends

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Abstract

The mechanism of the reductive homocoupling of pyridine derivatives mediated by the ZrII synthon [(PNP)Zr(η6-toluene)Cl] (1) has been investigated. Selective transformation into three different types of product complexes has been observed, depending on the N-heterocyclic substrate employed: the bipyridyl complexes 3-R (R = Me, Et, tBu, Bn, Ph, CHCHPh), which are the homocoupling products, the η2-((4-dimethylamino)pyridyl) complex 4 as well as the bis(isoquinolinyl) complex 5. By deuterium labelling experiments the participation of the ligand backbone in the pyridine coupling reaction via potential cyclometallation steps was ruled out. Based on DFT modelling of the possible reaction sequences a reaction mechanism for the coupling sequence could be identified. The latter is initiated by a reductive syn C–C coupling rather than based on an initial C–H activation of the pyridine substrate.

Graphical abstract: Dehydrogenative coupling of 4-substituted pyridines mediated by a zirconium(ii) synthon: reaction pathways and dead ends

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Publication details

The article was received on 03 Mar 2018, accepted on 15 May 2018 and first published on 16 May 2018


Article type: Edge Article
DOI: 10.1039/C8SC01025K
Citation: Chem. Sci., 2018,9, 5223-5232
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    Dehydrogenative coupling of 4-substituted pyridines mediated by a zirconium(II) synthon: reaction pathways and dead ends

    L. S. Merz, H. Wadepohl, E. Clot and L. H. Gade, Chem. Sci., 2018, 9, 5223
    DOI: 10.1039/C8SC01025K

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