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Catalytic asymmetric dipolar cycloadditions of indolyl delocalized metal-allyl species for the enantioselective synthesis of cyclopenta [b]indoles and pyrrolo[1,2-a]indoles

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Abstract

The development of novel synthons and efficient methods to synthesize chiral polycyclic indoles has been a hot topic in organic synthesis and medicinal chemistry owing to their broad applications in medicines, pesticides, and other functional molecules. Here, we disclosed novel indolyl substituted metal-allyl zwitterionic intermediates through the decarboxylation of conveniently available vinyl indoloxazolidones, which could be regarded as two types of dipolar species through the anionic delocalization. The palladium-π-allyl species tended to serve as an all-carbon 1,3-dipole in the asymmetric [3+2] cycloaddition with electron-deficient alkenes, which furnished polysubstituted cyclopenta[b]indoles with high regio- and stereoselectivities. Meanwhile, the iridium-π-allyl species was recognized as an aza-1,3-dipole in asymmetric [3+2] cycloaddition with in situ generated C1 ammonium enolates, affording pyrrolo[1,2-a]indoles with high diastereo- and enantioselectivities. In addition, the dipolar cycloadditions could be easily scaled-up and several synthetic transformations of the cycloadducts were demonstrated for the rapid synthesis of diverse chiral polycyclic indoles.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21901072), the China Postdoctoral Science Foundation (2019T120310) and Shanghai Sailing Program (18YF140560). Prof. Ying-Chun Chen of Sichuan University is acknowledged for helpful discussions. The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for the assistance with the HRMS and NMR analyses.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Shanghai Key Laboratory of New Drug Design and School of Pharmacy, East China University of Science and Technology, Shanghai, 200237, China

    Fei Tian, Wu-Lin Yang, Tao Ni, Jian Zhang & Wei-Ping Deng

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  1. Fei Tian
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  2. Wu-Lin Yang
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  3. Tao Ni
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  4. Jian Zhang
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  5. Wei-Ping Deng
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Correspondence to Wu-Lin Yang or Wei-Ping Deng.

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11426_2020_9854_MOESM1_ESM.pdf

Catalytic asymmetric dipolar cycloadditions of indolyl delocalized metal-allyl species for the enantioselective synthesis of cyclopenta [b]indoles and pyrrolo[1,2-a]indoles

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Supplementary material, approximately 228 KB.

Supplementary material, approximately 228 KB.

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Tian, F., Yang, WL., Ni, T. et al. Catalytic asymmetric dipolar cycloadditions of indolyl delocalized metal-allyl species for the enantioselective synthesis of cyclopenta [b]indoles and pyrrolo[1,2-a]indoles. Sci. China Chem. 64, 34–40 (2021). https://doi.org/10.1007/s11426-020-9854-3

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  • DOI: https://doi.org/10.1007/s11426-020-9854-3

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