Highly Regioselective Hydroaminomethylation of Terminal Olefins to Linear Amines Using Rh Complexes with a Tetrabi Phosphorus Ligand

Authors

  • Guodu Liu,

    1. College of Science, Northwest A & F University, Yangling, Shaanxi 712100 (P.R. China), Fax: (+86) 29 87093987
    2. Department of Chemistry and Chemical Biology and Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (USA), Fax: (+1) 732-445-6312
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  • Kexuan Huang,

    1. Department of Chemistry and Chemical Biology and Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (USA), Fax: (+1) 732-445-6312
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  • Chaoxian Cai,

    1. Department of Chemistry and Chemical Biology and Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (USA), Fax: (+1) 732-445-6312
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  • Bonan Cao,

    1. Department of Chemistry and Chemical Biology and Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (USA), Fax: (+1) 732-445-6312
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  • Mingxin Chang,

    1. Department of Chemistry and Chemical Biology and Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (USA), Fax: (+1) 732-445-6312
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  • Prof. Wenjun Wu,

    Corresponding author
    1. College of Science, Northwest A & F University, Yangling, Shaanxi 712100 (P.R. China), Fax: (+86) 29 87093987
    • College of Science, Northwest A & F University, Yangling, Shaanxi 712100 (P.R. China), Fax: (+86) 29 87093987
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  • Prof. Xumu Zhang

    Corresponding author
    1. Department of Chemistry and Chemical Biology and Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (USA), Fax: (+1) 732-445-6312
    • Department of Chemistry and Chemical Biology and Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (USA), Fax: (+1) 732-445-6312
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  • Tetrabi=2, 2′, 6, 6′-tetrakis ((diphenylphosphino)methyl)-1, 1′-biphenyl.

Abstract

A highly regioselective hydroaminomethylation of terminal olefins catalyzed by Rh complexes with 2, 2′, 6, 6′-tetrakis ((diphenylphosphino)methyl)-1, 1′-biphenyl (Tetrabi) ligand has been developed. Up to 99 % amine selectivity, 168 linear/branched amine product ratio (n/i), and 97.4 % linear amine yield has been obtained at a substrate/rhodium precursor ratio (S/Rh) of 1000 with this methodology. The turnover number was achieved 6930 at 10000 S/Rh ratio, and the n/i can reach up to >525. Several different olefins and secondary amines have been applied successfully with high chemoselectivity (99 %), yield (>98 %), and regioselectivity (>120).

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