Second-Generation Amino Acid Furanoside Based Ligands from D-Glucose for the Asymmetric Transfer Hydrogenation of Ketones

Authors

  • Dr. Mercedes Coll,

    1. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563
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  • Dr. Oscar Pàmies,

    Corresponding author
    1. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563
    • Oscar Pàmies, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563

      Hans Adolfsson, Department of Organic Chemistry, Stockholm University, Arrheniuslaboratoriet SE-106 91 Stockholm (Sweden), Fax: (+46) 08-154908

      Montserrat Diéguez, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563

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  • Prof. Hans Adolfsson,

    Corresponding author
    1. Department of Organic Chemistry, Stockholm University, Arrheniuslaboratoriet SE-106 91 Stockholm (Sweden), Fax: (+46) 08-154908
    • Oscar Pàmies, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563

      Hans Adolfsson, Department of Organic Chemistry, Stockholm University, Arrheniuslaboratoriet SE-106 91 Stockholm (Sweden), Fax: (+46) 08-154908

      Montserrat Diéguez, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563

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  • Prof. Montserrat Diéguez

    Corresponding author
    1. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563
    • Oscar Pàmies, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563

      Hans Adolfsson, Department of Organic Chemistry, Stockholm University, Arrheniuslaboratoriet SE-106 91 Stockholm (Sweden), Fax: (+46) 08-154908

      Montserrat Diéguez, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n. 43007 Tarragona (Spain), Fax: (+34) 977559563

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Abstract

A novel series of modular amino acid thioamide ligands functionalized with carbohydrates were introduced and employed in the rhodium-catalyzed asymmetric transfer hydrogenation (ATH) of aryl alkyl ketones, including the less-studied heteroaromatic ketones. The ligands are based on amino acid hydroxyamides (pseudodipeptides), which are the most successful ligands previously used in asymmetric hydrogen transfer reactions. High enantioselectivities [up to 99 % enantiomeric excess (ee)] were achieved in the ATH of a wide range of aryl alkyl ketones by using catalysts generated in situ from [RhCl2Cp*]2 (Cp*=C5Me5) and thioamide ligands comprising a 3-benzyl glucofuranoside backbone and a bulky isopropyl group in the α-amino acid moiety. Interestingly, both enantiomers of the alcohol products can readily be obtained with high enantioselectivity by simply changing the absolute configuration of the α-amino acid. The good performance can be extended to a very challenging class of industrially interesting heteroaromatic ketones (up to 99 % ee).

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