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Enantioselective cyanation via radical-mediated C–C single bond cleavage for synthesis of chiral dinitriles

Author

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  • Tao Wang

    (Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China)

  • Yi-Ning Wang

    (Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China)

  • Rui Wang

    (Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China)

  • Bo-Chao Zhang

    (Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China)

  • Chi Yang

    (Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China)

  • Yan-Lin Li

    (Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China)

  • Xi-Sheng Wang

    (Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China)

Abstract

Ring-opening reaction via selective cleavage of C–C bond is known as a powerful strategy for construction of complex molecules. Complementary to the ionic process focusing on mostly small ring systems, radical-mediated C–C bond cleavage offers a solution for further diverse enantioselective functionalization benefited from its mild conditions, whereas such asymmetric transformations are still limited to three-membered rings so far. Herein, we describe radical-mediated ring-opening and enantioselective cyanation of four- and five-membered cycloketone oxime esters to access chiral 1,5- and 1,6-dinitriles. Employment of dual photoredox/copper catalysis is essential for the asymmetric ring-opening cyanation of cyclopentanone oxime esters. Both reactions proceed under mild conditions giving chiral dinitriles in high yields and enantioselectivity with low catalyst loading and broad substrate scope. The products dinitriles can be converted to valuable optically active diamides and diamines. Mechanistic studies indicate that the benzylic radical generated via C–C single bond cleavage is involved in the catalytic cycle.

Suggested Citation

  • Tao Wang & Yi-Ning Wang & Rui Wang & Bo-Chao Zhang & Chi Yang & Yan-Lin Li & Xi-Sheng Wang, 2019. "Enantioselective cyanation via radical-mediated C–C single bond cleavage for synthesis of chiral dinitriles," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-13369-x
    DOI: 10.1038/s41467-019-13369-x
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    Cited by:

    1. Rupeng Qi & Qiao Chen & Liangyu Liu & Zijian Ma & Da Pan & Hongying Wang & Zhixuan Li & Chao Wang & Zhaoqing Xu, 2023. "Copper-catalyzed asymmetric C(sp3)-H cyanoalkylation of glycine derivatives and peptides," Nature Communications, Nature, vol. 14(1), pages 1-9, December.

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