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Alkoxycarbonylpiperidines as N-nucleophiles in the palladium-catalyzed aminocarbonylation

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Abstract

Piperidines possessing ester functionality, such as 2-(methoxycarbonyl)piperidine (methyl pipecolinate), 3-(ethoxycarbonyl)piperidine (ethyl nipecotate), and 4-(ethoxycarbonyl)piperidine (ethyl isonipecotate), were used as N-nucleophiles in palladium-catalyzed aminocarbonylation of iodobenzene and iodoalkenes such as 1-iodocyclohexene and 17-iodoandrost-16-ene. While the aminocarbonylation of both iodoalkenes, carried out under mild reaction conditions, resulted in the exclusive formation of the carboxamide, the same reaction of iodobenzene brought about the mixture of the corresponding carboxamide and 2-ketocarboxamide. The chemoselectivity toward the latter compounds, formed via double carbonyl insertion, was substantially increased by using high carbon monoxide pressure (up to 40 bar). Carboxamides derived from iodoalkenes and ketocarboxamides derived from iodoarene have been obtained in moderate to high yields.

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Acknowledgments

The authors thank the project ‘Synthesis of supramolecular systems, examination of their physicochemical properties and their utilization for separation and sensor chemistry’ (SROP-4.2.2.A-11/1/KONV-2012-0065) for the financial support. This research of A. T. was supported by the European Union and the State of Hungary, co-financed by the European Social Fund in the framework of TÁMOP 4.2.4. A/2-11-1-2012-0001 ‘National Excellence Program’.

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Authors and Affiliations

  1. MTA-PTE Research Group for Selective Chemical Syntheses, Ifjúság u. 6, 7624, Pecs, Hungary

    Attila Takács & László Kollár

  2. Department of Inorganic Chemistry, University of Pécs and Szentágothai Research Centre, P.O. Box 266, 7624, Pecs, Hungary

    Zsuzsanna Kabak-Solt, Gábor Mikle & László Kollár

Authors
  1. Attila Takács
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  2. Zsuzsanna Kabak-Solt
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  3. Gábor Mikle
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  4. László Kollár
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Correspondence to László Kollár.

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Takács, A., Kabak-Solt, Z., Mikle, G. et al. Alkoxycarbonylpiperidines as N-nucleophiles in the palladium-catalyzed aminocarbonylation. Monatsh Chem 145, 1473–1478 (2014). https://doi.org/10.1007/s00706-014-1254-1

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  • DOI: https://doi.org/10.1007/s00706-014-1254-1

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