Asymmetric Hydrogenation of 2,4-Disubstituted 1,5-Benzodiazepines Using Cationic Ruthenium Diamine Catalysts: An Unusual Achiral Counteranion Induced Reversal of Enantioselectivity

Authors

  • Zi-Yuan Ding,

    1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry and Graduate School, Chinese Academy of Sciences (CAS), Beijing 100190 (P. R. China)
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  • Fei Chen,

    1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry and Graduate School, Chinese Academy of Sciences (CAS), Beijing 100190 (P. R. China)
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  • Jie Qin,

    1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry and Graduate School, Chinese Academy of Sciences (CAS), Beijing 100190 (P. R. China)
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  • Yan-Mei He,

    1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry and Graduate School, Chinese Academy of Sciences (CAS), Beijing 100190 (P. R. China)
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  • Prof. Dr. Qing-Hua Fan

    Corresponding author
    1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry and Graduate School, Chinese Academy of Sciences (CAS), Beijing 100190 (P. R. China)
    • Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry and Graduate School, Chinese Academy of Sciences (CAS), Beijing 100190 (P. R. China)
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  • Financial support from the National Basic Research Program of China (973 Program, Nos. 2010CB833300 and 2011CB808600), the National Natural Science Foundation of China (Grant No 20973178), and the Chinese Academy of Sciences is greatly acknowledged.

Abstract

original image

BArFing it out the other way: A highly enantioselective hydrogenation of 2,4-disubstituted 1,5-benzodiazepines using chiral cationic ruthenium diamine catalysts (R,R)-1 has been developed (see scheme; BArF=tetrakis(3,5-bistrifluoromethylphenyl)borate). Either enantiomer of 2,4-diaryl-2,3,4,5-tetrahydro-1H-benzodiazepine derivatives could be obtained by using the same enantiomer of ligand but in the presence of a different achiral counteranion.

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