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NHC-catalyzed enantioselective access to β-cyano carboxylic esters via in situ substrate alternation and release

Author

Listed:
  • Qingyun Wang

    (Guizhou University)

  • Shuquan Wu

    (Guizhou Minzu University)

  • Juan Zou

    (Guizhou University of Traditional Chinese Medicine)

  • Xuyang Liang

    (Guizhou University)

  • Chengli Mou

    (Guizhou University of Traditional Chinese Medicine)

  • Pengcheng Zheng

    (Guizhou University)

  • Yonggui Robin Chi

    (Guizhou University
    Nanyang Technological University)

Abstract

A carbene-catalyzed asymmetric access to chiral β-cyano carboxylic esters is disclosed. The reaction proceeds between β,β-disubstituted enals and aromatic thiols involving enantioselective protonation of enal β-carbon. Two main factors contribute to the success of this reaction. One involves in situ ultrafast addition of the aromatic thiol substrates to the carbon-carbon double bond of the enal substrate. This reaction converts almost all enal substrate to a Thiol-click Intermediate, significantly reducing aromatic thiol substrates concentration and suppressing the homo-coupling reaction of enals. Another factor is an in situ release of enal substrate from the Thiol-click Intermediate for the desired reaction to proceed effectively. The optically enriched β-cyano carboxylic esters from our method can be readily transformed to medicines that include γ-aminobutyric acids derivatives such as Rolipram. In addition to synthetic utilities, our control of reaction outcomes via in situ substrate modulation and release can likely inspire future reaction development.

Suggested Citation

  • Qingyun Wang & Shuquan Wu & Juan Zou & Xuyang Liang & Chengli Mou & Pengcheng Zheng & Yonggui Robin Chi, 2023. "NHC-catalyzed enantioselective access to β-cyano carboxylic esters via in situ substrate alternation and release," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-40645-8
    DOI: 10.1038/s41467-023-40645-8
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    References listed on IDEAS

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    1. Matthew N. Hopkinson & Christian Richter & Michael Schedler & Frank Glorius, 2014. "An overview of N-heterocyclic carbenes," Nature, Nature, vol. 510(7506), pages 485-496, June.
    2. Ya Lv & Guoyong Luo & Qian Liu & Zhichao Jin & Xinglong Zhang & Yonggui Robin Chi, 2022. "Catalytic atroposelective synthesis of axially chiral benzonitriles via chirality control during bond dissociation and CN group formation," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    3. Zachary C. Litman & Yajie Wang & Huimin Zhao & John F. Hartwig, 2018. "Cooperative asymmetric reactions combining photocatalysis and enzymatic catalysis," Nature, Nature, vol. 560(7718), pages 355-359, August.
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    Cited by:

    1. Shao-Qing Shi & Chen-Chang Cui & Lin-Lin Xu & Jin-Peng Zhang & Wen-Juan Hao & Jianyi Wang & Bo Jiang, 2024. "Enantioselective synthesis of saddle-shaped eight-membered lactones with inherent chirality via organocatalytic high-order annulation," Nature Communications, Nature, vol. 15(1), pages 1-11, December.

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