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Catalytic Asymmetric Arylation of Enals to Enantioenriched Linear Trisubstituted Allylic Secondary Alcohols by using Aryl Lithiums Generated In Situ from Aryl Bromides

Authors

  • Lei Zhang,

    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
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    • These authors contributed equally to this work.

  • Lin Sun,

    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
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    • These authors contributed equally to this work.

  • Yu-Yan Li,

    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
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  • Yue Liu,

    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
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  • Yong-Xin Yang,

    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
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  • Rui Yuan,

    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
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  • Pei Wang,

    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
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  • Prof. Dr. Chao-Shan Da

    Corresponding author
    1. Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208
    2. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China)
    3. Key Lab of Preclinical Study for New Drugs of Gansu Province, Lanzhou University, Lanzhou 730000 (China)
    • Institute of Biochemistry & Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5208

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Abstract

Catalytic asymmetric addition of nucleophiles to enals is a straightforward method towards enantioenriched allylic alcohols, which are important for the synthesis of natural and pharmaceutically active compounds. Reactive aryl lithiums, produced in situ from readily available and inexpensive aryl bromides and butyl lithium, were used to enantioselectively arylate a number of α-substituted cinnamaldehydes in the presence of tetramethylethylenediamine (TMEDA), AlCl3, and Ti(OiPr)4. This enabled enantioenriched linear trisubstituted allylic secondary alcohols in the catalysis of (S)-H8-BINOL-(TiOiPr)2 complex. TMEDA coordinated the lithium salt generated in situ during transmetallation and effectively inhibited the unwanted background reaction catalyzed by the Lewis acidic lithium salt.

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