Synthesis of Chiral Cyclic Nitrones by Asymmetric Addition of β-Ketosulfones to Nitroalkenes followed by Reductive Cyclization

Authors

  • Dr. Olga García Mancheño,

    Corresponding author
    1. Organisch-Chemisches Institut, Westfälischen Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-8333202
    • Organisch-Chemisches Institut, Westfälischen Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-8333202
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  • Pia Tangen,

    1. Departamento de Química Orgánica (C-I), Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 914973875
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  • Renate Rohlmann,

    1. Organisch-Chemisches Institut, Westfälischen Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-8333202
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  • Roland Fröhlich,

    1. Organisch-Chemisches Institut, Westfälischen Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-8333202
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  • Dr. José Alemán

    Corresponding author
    1. Departamento de Química Orgánica (C-I), Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 914973875
    • Departamento de Química Orgánica (C-I), Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 914973875
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Abstract

The first organocatalytic addition of β-ketosulfones to nitroalkenes catalyzed by thiourea cinchona alkaloids is presented. The readily obtained addition products were selectively transformed into chiral nitrones by reduction of the nitro group and in situ cyclization (up to 99:1 e.r. and >98:2 d.r.). Moreover, the utility of this method has additionally been demonstrated by the further transformation to functionalized N-hydroxypyrrolidines that possess a quaternary center by addition of trimethylsilyl cyanide (TMSCN) to the C[DOUBLE BOND]N bond of the cyclic nitrones in the presence of a Lewis acid.

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