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Radical asymmetric intramolecular α-cyclopropanation of aldehydes towards bicyclo[3.1.0]hexanes containing vicinal all-carbon quaternary stereocenters

Author

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  • Liu Ye

    (South University of Science and Technology of China)

  • Qiang-Shuai Gu

    (South University of Science and Technology of China)

  • Yu Tian

    (South University of Science and Technology of China)

  • Xiang Meng

    (South University of Science and Technology of China)

  • Guo-Cong Chen

    (South University of Science and Technology of China)

  • Xin-Yuan Liu

    (South University of Science and Technology of China)

Abstract

The development of a general catalytic method for the direct and stereoselective construction of cyclopropanes bearing highly congested vicinal all-carbon quaternary stereocenters remains a formidable challenge in chemical synthesis. Here, we report an intramolecular radical cyclopropanation of unactivated alkenes with simple α-methylene group of aldehydes as C1 source via a Cu(I)/secondary amine cooperative catalyst, which enables the single-step construction of bicyclo[3.1.0]hexane skeletons with excellent efficiency, broad substrate scope covering various terminal, internal alkenes as well as diverse (hetero)aromatic, alkenyl, alkyl-substituted geminal alkenes. Moreover, this reaction has been successfully realized to an asymmetric transformation, providing an attractive approach for the construction of enantioenriched bicyclo[3.1.0]hexanes bearing two crucial vicinal all-carbon quaternary stereocenters with good to excellent enantioselectivity. The utility of this method is illustrated by facile transformations of the products into various useful chiral synthetic intermediates. Preliminary mechanistic studies support a stepwise radical process for this formal [2 + 1] cycloaddition.

Suggested Citation

  • Liu Ye & Qiang-Shuai Gu & Yu Tian & Xiang Meng & Guo-Cong Chen & Xin-Yuan Liu, 2018. "Radical asymmetric intramolecular α-cyclopropanation of aldehydes towards bicyclo[3.1.0]hexanes containing vicinal all-carbon quaternary stereocenters," Nature Communications, Nature, vol. 9(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-017-02231-7
    DOI: 10.1038/s41467-017-02231-7
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