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Issue 10, 2015
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RhI/RhIII catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes

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Abstract

The ability to establish switchable site-selectivity through catalyst control in the direct functionalization of molecules that contain distinct C–H bonds remains a demanding challenge that would enable the construction of diverse scaffolds from the same starting materials. Herein we describe the realization of this goal, namely a divergent heteroaryl/aryl C–H functionalization of aromatic picolinamide derivatives, targeting two distinct C–H sites, either at the pyridine ring or at the arene unit, to afford isoquinoline or ortho-olefinated benzylamine (or phenethylamine) derivatives. This complementary reactivity has been achieved on the basis of a RhIII/RhI switch in the catalyst, resulting in different mechanistic outcomes. Notably, a series of experimental and DFT mechanistic studies revealed important insights about the mechanism of the reaction and reasons behind the divergent regiochemical outcome.

Graphical abstract: RhI/RhIII catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes

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Publication details

The article was received on 25 May 2015, accepted on 27 Jun 2015 and first published on 29 Jun 2015


Article type: Edge Article
DOI: 10.1039/C5SC01885D
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Citation: Chem. Sci., 2015,6, 5802-5814
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    RhI/RhIII catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes

    Á. M. Martínez, J. Echavarren, I. Alonso, N. Rodríguez, R. Gómez Arrayás and J. C. Carretero, Chem. Sci., 2015, 6, 5802
    DOI: 10.1039/C5SC01885D

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