Enantiopure Triazolium Salts: Chemoenzymatic Synthesis and Applications in Organocatalysis

Authors

  • Nicolás Ríos-Lombardía,

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Biotecnología de Asturias, Universidad de Oviedo, Avenida Julián Clavería s/n, Oviedo 33006 (Spain), Fax: (+34) 985-103448
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  • Raúl Porcar,

    1. Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Av. de Vicent Sos Baynat s/n, Castellón de la Plana 12071 (Spain), Fax: (+34)964-728214
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  • Dr. Eduardo Busto,

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Biotecnología de Asturias, Universidad de Oviedo, Avenida Julián Clavería s/n, Oviedo 33006 (Spain), Fax: (+34) 985-103448
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  • Dr. Ignacio Alfonso,

    1. Departamento de Química Biológica y Modelización Molecular, Instituto de Química Avanzada de Cataluña (IQAC-CSIC), Calle Jordi Girona 18-26, Barcelona 08034 (Spain)
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  • Dr. Jose Montejo-Bernardo,

    1. Departamento de Química Física y Analítica, Universidad de Oviedo, Avenida Julián Clavería s/n, Oviedo 33006 (Spain)
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  • Prof. Santiago García-Granda,

    1. Departamento de Química Física y Analítica, Universidad de Oviedo, Avenida Julián Clavería s/n, Oviedo 33006 (Spain)
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  • Prof. Vicente Gotor,

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Biotecnología de Asturias, Universidad de Oviedo, Avenida Julián Clavería s/n, Oviedo 33006 (Spain), Fax: (+34) 985-103448
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  • Prof. Santiago V. Luis,

    1. Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Av. de Vicent Sos Baynat s/n, Castellón de la Plana 12071 (Spain), Fax: (+34)964-728214
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  • Dr. Eduardo García-Verdugo,

    Corresponding author
    1. Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Av. de Vicent Sos Baynat s/n, Castellón de la Plana 12071 (Spain), Fax: (+34)964-728214
    • Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Av. de Vicent Sos Baynat s/n, Castellón de la Plana 12071 (Spain), Fax: (+34)964-728214
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  • Dr. Vicente Gotor-Fernández

    Corresponding author
    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Biotecnología de Asturias, Universidad de Oviedo, Avenida Julián Clavería s/n, Oviedo 33006 (Spain), Fax: (+34) 985-103448
    • Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Biotecnología de Asturias, Universidad de Oviedo, Avenida Julián Clavería s/n, Oviedo 33006 (Spain), Fax: (+34) 985-103448
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Abstract

A novel family of triazolium salt enantiomers has been efficiently synthesized by combining chemical and biocatalytic methods. The stereoselective action shown by hydrolytic enzymes led to the design of simple and general chemoenzymatic routes in which tunable vectors, such as ring size, substituent stereochemistry, oxygen substitution, anion nature, or N4-triazole alkylating chain, were considered to produce 30 enantiopure triazolium salts in very high overall yields. Finally, selected triazolium salts were tested as phase-transfer catalysts in the asymmetric Michael addition of diethyl malonate to trans-chalcone to rationalize their activity and stereopreference. Low to complete conversion values were achieved in the formation of the Michael addition adduct, which mainly gave low levels of stereoselectivity depending on the different structural patterns considered in this systematic study.

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