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Silver-catalyzed unstrained C(CO)-alkyl bond scission via [3+2]/retro-[3+2] cycloaddition of ketones with N-isocyanoiminotriphenylphosphorane

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Abstract

C(CO)-alkyl bonds are ubiquitous in a variety of organic molecules, and their selective activation and functionalization are important for the reconstruction of simple ketones into valuable building blocks. However, due to the thermodynamic and kinetic stability, the cleavage and transformation of the unstrained C(CO)-alkyl bonds remain a significant challenge. Herein, we report a novel silver-catalyzed scission of the unstrained C(CO)-alkyl bond of ketones by reacting with N-isocyanoiminotriphenylphosphorane (NIITP) under mild conditions. This method could transform a variety of unstrained ketones into iminophosphoranes and nitriles in high yields. Experimental and computational studies disclosed the reaction proceeded through an unprecedented [3+2]/retro-[3+2] cycloaddition mechanism.

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Acknowledgements

This work was provided by the National Natural Science Foundation of China (21871043, 21961130376), Department of Science and Technology of Jilin Province (20180101185JC, 20190701012GH, 20200801065GH), and the Fundamental Research Funds for the Central Universities (2412019ZD001, 2412019FZ006).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Northeast Normal University, Changchun, 130024, China

    Zikun Wang, Linxuan Li, Xueying Zhang & Xihe Bi

  2. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, China

    Xihe Bi

Authors
  1. Zikun Wang
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  2. Linxuan Li
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  3. Xueying Zhang
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  4. Xihe Bi
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Correspondence to Xihe Bi.

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Silver-catalyzed unstrained C(CO)-alkyl bond scission via [3+2]/retro-[3+2] cycloaddition of ketones with N-isocyanoiminotriphenylphosphorane

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Wang, Z., Li, L., Zhang, X. et al. Silver-catalyzed unstrained C(CO)-alkyl bond scission via [3+2]/retro-[3+2] cycloaddition of ketones with N-isocyanoiminotriphenylphosphorane. Sci. China Chem. 64, 1157–1163 (2021). https://doi.org/10.1007/s11426-021-1000-8

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  • DOI: https://doi.org/10.1007/s11426-021-1000-8

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