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Carbon-silicon-switch effect in enantioselective construction of silicon-stereogenic center from silacyclohexadienones

Author

Listed:
  • Yu Yan

    (Chengdu University
    Inner Mongolia University)

  • Qi Wei

    (Sichuan University)

  • Zhishan Su

    (Sichuan University)

  • Nan-Nan Hang

    (Inner Mongolia University)

  • Tamio Hayashi

    (National Taiwan Normal University)

  • Jialin Ming

    (Chengdu University
    Inner Mongolia University)

Abstract

Carbon-silicon-switch strategy, replacing one specific carbon atom in organic molecules with a silicon, has garnered significant interest for developing new functional molecules. However, the influence of a reaction regarding its selectivity and reactivity by carbon-silicon-switch strategy has far less been investigated. Here we discover an unusual carbon-silicon-switch effect in the enantioselective construction of silicon-stereogenic center. It is found that there has been a significant change in the desymmetrization reaction of silacyclohexadienones using asymmetric conjugate addition or oxidative Heck reaction with aryl/alkyl nucleophiles when compared with their carbon analogues cyclohexadienones. Specifically, the carbon-silicon-switch leads to a reversal in enantioselectivity with arylzinc as the nucleophile by the same chiral catalyst, and results in totally different reactivity with arylboronic acid as the nucleophile. Control experiments and density functional theory (DFT) calculations have shown that the unusual carbon-silicon-switch effect comes from the unique stereoelectronic feature of silicon.

Suggested Citation

  • Yu Yan & Qi Wei & Zhishan Su & Nan-Nan Hang & Tamio Hayashi & Jialin Ming, 2024. "Carbon-silicon-switch effect in enantioselective construction of silicon-stereogenic center from silacyclohexadienones," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-54241-x
    DOI: 10.1038/s41467-024-54241-x
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    References listed on IDEAS

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    1. Shuyou Chen & Delong Mu & Pei-Lin Mai & Jie Ke & Yingzi Li & Chuan He, 2021. "Enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    2. Xi-Chao Wang & Bo Li & Cheng-Wei Ju & Dongbing Zhao, 2022. "Nickel(0)-catalyzed divergent reactions of silacyclobutanes with internal alkynes," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    3. Xihong Wang & Chi Feng & Julong Jiang & Satoshi Maeda & Koji Kubota & Hajime Ito, 2023. "Stereospecific synthesis of silicon-stereogenic optically active silylboranes and general synthesis of chiral silyl Anions," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    4. Honggui Lv & Huiying Kang & Biying Zhou & Xiaosong Xue & Keary M. Engle & Dongbing Zhao, 2019. "Nickel-catalyzed intermolecular oxidative Heck arylation driven by transfer hydrogenation," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    5. Tianbao Hu & Chen Zhao & Yan Zhang & Yuzhong Kuang & Lu Gao & Wanshu Wang & Zhishan Su & Zhenlei Song, 2023. "Enantioconvergent construction of stereogenic silicon via Lewis base-catalyzed dynamic kinetic silyletherification of racemic chlorosilanes," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
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