Functionalization of Non-activated C[BOND]H Bonds of Alkanes: An Effective and Recyclable Catalytic System Based on Fluorinated Silver Catalysts and Solvents

Authors

  • M. Ángeles Fuentes,

    1. Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible (CIQSO), Campus de El Carmen s/n, Universidad de Huelva, 21007-Huelva (Spain), Fax: (+34) 959219942
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  • Dr. Bianca K. Muñoz,

    1. CNRS; LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP44099, F-31077 Toulouse Cedex 4 (France)
    2. Université de Toulouse, UPS, INPT; LCC, F-31077 Toulouse Cedex 4 (France)
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  • Kane Jacob,

    1. CNRS; LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP44099, F-31077 Toulouse Cedex 4 (France)
    2. Université de Toulouse, UPS, INPT; LCC, F-31077 Toulouse Cedex 4 (France)
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  • Dr. Laure Vendier,

    1. CNRS; LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP44099, F-31077 Toulouse Cedex 4 (France)
    2. Université de Toulouse, UPS, INPT; LCC, F-31077 Toulouse Cedex 4 (France)
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  • Dr. Ana Caballero,

    Corresponding author
    1. Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible (CIQSO), Campus de El Carmen s/n, Universidad de Huelva, 21007-Huelva (Spain), Fax: (+34) 959219942
    • Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible (CIQSO), Campus de El Carmen s/n, Universidad de Huelva, 21007-Huelva (Spain), Fax: (+34) 959219942
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  • Prof. Michel Etienne,

    Corresponding author
    1. CNRS; LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP44099, F-31077 Toulouse Cedex 4 (France)
    2. Université de Toulouse, UPS, INPT; LCC, F-31077 Toulouse Cedex 4 (France)
    • CNRS; LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP44099, F-31077 Toulouse Cedex 4 (France)
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  • Prof. Pedro J. Pérez

    Corresponding author
    1. Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible (CIQSO), Campus de El Carmen s/n, Universidad de Huelva, 21007-Huelva (Spain), Fax: (+34) 959219942
    • Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible (CIQSO), Campus de El Carmen s/n, Universidad de Huelva, 21007-Huelva (Spain), Fax: (+34) 959219942
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Abstract

The complexes Fn-Tpmath imageAg(L) (Fn-Tpmath image=a perfluorinated hydrotris(indazolyl) borate ligand; L=acetone or tetrahydrofuran) efficiently catalyze the functionalization of non-activated alkanes such as hexane, 2,3-dimethylbutane, or 2-methylpentane by insertion of CHCO2Et units (from N2CHCO2Et, ethyl diazoacetate, EDA) into their C[BOND]H bonds. The reactions are quantitative (EDA-based), with no byproducts derived from diazo coupling being formed. In the case of hexane, the functionalization of the methyl C[BOND]H bonds has been achieved with the highest regioselectivity known to date with this diazo compound. This catalytic system also operates under biphasic conditions by using fluorous solvents such as Fomblin or perfluorophenanthrene. Several cycles of catalyst recovery and reuse have been performed, with identical chemo- and regioselectivities.

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