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Regioselective hydrolysis of ketenimines derived from NH-acids and acetylenic esters in the presence of tert-butyl isocyanide under neutral conditions

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Abstract

The regioselective hydrolysis of ketenimines derived from NH-acids, such as 2,2,2-trichloro-N-phenylacetamide or ethyl-2-anilino-2-oxoacetates and acetylenic esters in the presence of tert-butyl isocyanide in a THF/H2O system (1/1) without any catalysis leads to a diastereomeric mixture of dialkyl 2-[(tert-butylamino)carbonyl]-3-[(2,2,2-trichloroacetyl)anilino]succinates and dialkyl 2-[(tert-butylamino)carbonyl]-3-[2-ethoxy-2-oxoacetyl)anilino]-succinates in good yields. Dynamic NMR effects were observed in the 13C NMR spectra of diethyl 2-[(tert-butylamino)carbonyl]-3-[(2,2,2-trichloroacetyl)anilino]succinate as a result of restricted rotation around the N-aryl single bond. The free energy of activation (ΔG #) for this process is 37.9 kJ mol−1 which leads to an observable atropisomerism.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Sciences, University of Kurdistan, Sanandaj, Iran

    Farough Nasiri & Samiyeh Yosefdad

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  1. Farough Nasiri
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  2. Samiyeh Yosefdad
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Correspondence to Farough Nasiri.

Additional information

Correspondence: Dr. Farough Nasiri PhD, Department of Chemistry, Faculty of Sciences, University of Kurdistan, P.O. Box 66315-416, Sanandaj, Iran.

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Nasiri, F., Yosefdad, S. Regioselective hydrolysis of ketenimines derived from NH-acids and acetylenic esters in the presence of tert-butyl isocyanide under neutral conditions. Monatsh Chem 139, 1457–1461 (2008). https://doi.org/10.1007/s00706-008-0954-9

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  • DOI: https://doi.org/10.1007/s00706-008-0954-9

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