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Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations

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Abstract

Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

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Acknowledgments

We thank IKERBASQUE, Basque Foundation for Science; Basque Government (SAIOTEK S-PE12UN044) and Hamari Chemicals (Osaka, Japan) for generous financial support.

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The authors declare that they have no conflict of interest.

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Authors and Affiliations

  1. Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, 20018, San Sebastián, Spain

    Alexander E. Sorochinsky, José Luis Aceña & Vadim A. Soloshonok

  2. IKERBASQUE, Basque Foundation for Science, 48011, Bilbao, Spain

    Alexander E. Sorochinsky & Vadim A. Soloshonok

  3. Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Murmanska 1, Kyiv, 02660, Ukraine

    Alexander E. Sorochinsky

  4. Hamari Chemicals Ltd, 1-4-29 Kunijima, Higashi-Yodogawa-ku, Osaka, 533-0024, Japan

    Hiroki Moriwaki & Tatsunori Sato

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  1. Alexander E. Sorochinsky
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  2. José Luis Aceña
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  3. Hiroki Moriwaki
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  4. Tatsunori Sato
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  5. Vadim A. Soloshonok
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Correspondence to Vadim A. Soloshonok.

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Sorochinsky, A.E., Aceña, J.L., Moriwaki, H. et al. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations. Amino Acids 45, 691–718 (2013). https://doi.org/10.1007/s00726-013-1539-4

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