Use of Hemilabile N,N Ligands in Nitrogen-Directed Iridium-Catalyzed Borylations of Arenes

Authors

  • Dr. Abel Ros,

    1. Instituto de Investigaciones Químicas (CSIC-US), Américo Vespucio 49, 41092 Seville (Spain)
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  • Beatriz Estepa,

    1. Departamento de Química Orgánica, Universidad de Sevilla, C/Prof. García González, 1, 41012 Sevilla (Spain)
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  • Rocío López-Rodríguez,

    1. Instituto de Investigaciones Químicas (CSIC-US), Américo Vespucio 49, 41092 Seville (Spain)
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  • Dr. Eleuterio Álvarez,

    1. Instituto de Investigaciones Químicas (CSIC-US), Américo Vespucio 49, 41092 Seville (Spain)
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  • Prof. Rosario Fernández,

    Corresponding author
    1. Departamento de Química Orgánica, Universidad de Sevilla, C/Prof. García González, 1, 41012 Sevilla (Spain)
    • Departamento de Química Orgánica, Universidad de Sevilla, C/Prof. García González, 1, 41012 Sevilla (Spain)
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  • Dr. José M. Lassaletta

    Corresponding author
    1. Instituto de Investigaciones Químicas (CSIC-US), Américo Vespucio 49, 41092 Seville (Spain)
    • Instituto de Investigaciones Químicas (CSIC-US), Américo Vespucio 49, 41092 Seville (Spain)
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  • We thank the Spanish “Ministerio de Ciencia e Innovación” (grants CTQ2010-15297 and CTQ2010-14974, and fellowship to B.E.), the European FEDER funds and the Junta de Andalucía (grants 2008/FQM-3833 and 2009/FQM-4537) for financial support. A.R. thanks the EU for a Marie Curie Reintegration Grant (FP7-PEOPLE-2009-RG-256461) and R.L.-R. thanks CSIC for a JAE predoctoral fellowship.

Abstract

original image

The hemilabile character of 2-pyridyl carbaldehyde hydrazones as N,N bidentate ligands is key to performing regioselective IrIII-catalyzed ortho borylations of 2-aryl pyridines(isoquinolines) and aromatic N,N-dimethylhydrazones (see scheme; pin=pinacol, Bn=benzyl). Internal “ate” complexes or products free from N[BOND]B interactions are formed depending on the steric properties of the substrates.

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