Modification of (1R,2S)-1,2-Diphenyl-2-aminoethanol for the Highly Enantioselective, Asymmetric Alkylation of N-Diphenylphosphinoyl Arylimines with Dialkylzinc

Authors

  • Hai-Le Zhang,

    1. Key Laboratory for Asymmetric Synthesis and Chirotechnology, of Sichuan Province, Chengdu Institute of Organic Chemistry Chinese Academy, of Sciences, Chengdu, 610041, China, Fax: (+86) 28-8522-3978
    Search for more papers by this author
  • Fan Jiang,

    1. State Key Laboratory of Molecular Dynamics and Stable Species, College of Chemistry, Peking University, Beijing, China
    Search for more papers by this author
  • Xiao-Mei Zhang,

    1. Key Laboratory for Asymmetric Synthesis and Chirotechnology, of Sichuan Province, Chengdu Institute of Organic Chemistry Chinese Academy, of Sciences, Chengdu, 610041, China, Fax: (+86) 28-8522-3978
    Search for more papers by this author
  • Xin Cui,

    1. Key Laboratory for Asymmetric Synthesis and Chirotechnology, of Sichuan Province, Chengdu Institute of Organic Chemistry Chinese Academy, of Sciences, Chengdu, 610041, China, Fax: (+86) 28-8522-3978
    Search for more papers by this author
  • Liu-Zhu Gong Prof.,

    1. Key Laboratory for Asymmetric Synthesis and Chirotechnology, of Sichuan Province, Chengdu Institute of Organic Chemistry Chinese Academy, of Sciences, Chengdu, 610041, China, Fax: (+86) 28-8522-3978
    Search for more papers by this author
  • Ai-Qiao Mi Prof.,

    1. Key Laboratory for Asymmetric Synthesis and Chirotechnology, of Sichuan Province, Chengdu Institute of Organic Chemistry Chinese Academy, of Sciences, Chengdu, 610041, China, Fax: (+86) 28-8522-3978
    Search for more papers by this author
  • Yao-Zhong Jiang,

    1. Key Laboratory for Asymmetric Synthesis and Chirotechnology, of Sichuan Province, Chengdu Institute of Organic Chemistry Chinese Academy, of Sciences, Chengdu, 610041, China, Fax: (+86) 28-8522-3978
    Search for more papers by this author
  • Yun-Dong Wu Prof.

    1. State Key Laboratory of Molecular Dynamics and Stable Species, College of Chemistry, Peking University, Beijing, China
    2. Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
    Search for more papers by this author

Abstract

Experimental studies on the modification of (1R,2S)-1,2-diphenyl-2-aminoethanol, which is used to promote the alkylation of N-diphenylphosphinoyl benzalimine with diethylzinc, revealed that N-monosubstituted amino alcohols exhibited higher enantioselectivities than their N,N-disubstituted counterparts and imino alcohols. Application of the optimal chiral ligand 3 c to activate the reaction of N-diphenylphosphinoyl arylimines with diethylzinc and dibutylzinc resulted in excellent enantiomeric selectivities of up to 98 % ee. The origin of the experimentally observed enantioselectivities was revealed by density functional calculations (B3LYP/6-31G*) on the transition structures of several model reactions.

Ancillary