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Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C(sp3)−H bonds with alkynes

Author

Listed:
  • Zhen-Hua Zhang

    (Linyi University
    Southern University of Science and Technology)

  • Xiao-Yang Dong

    (Southern University of Science and Technology)

  • Xuan-Yi Du

    (Southern University of Science and Technology)

  • Qiang-Shuai Gu

    (Southern University of Science and Technology)

  • Zhong-Liang Li

    (Southern University of Science and Technology)

  • Xin-Yuan Liu

    (Southern University of Science and Technology)

Abstract

Transition metal-catalyzed enantioselective Sonogashira-type oxidative C(sp3)—C(sp) coupling of unactivated C(sp3)−H bonds with terminal alkynes has remained a prominent challenge. The difficulties mainly stem from the regiocontrol in unactivated C(sp3)—H bond functionalization and the inhibition of readily occurring Glaser homocoupling of terminal alkynes. Here, we report a copper/chiral cinchona alkaloid-based N,N,P-ligand catalyst for asymmetric oxidative cross-coupling of unactivated C(sp3)—H bonds with terminal alkynes in a highly regio-, chemo-, and enantioselective manner. The use of N-fluoroamide as a mild oxidant is essential to site-selectively generate alkyl radical species while efficiently avoiding Glaser homocoupling. This reaction accommodates a range of (hetero)aryl and alkyl alkynes; (hetero)benzylic and propargylic C(sp3)−H bonds are all applicable. This process allows expedient access to chiral alkynyl amides/aldehydes. More importantly, it also provides a versatile tool for the construction of chiral C(sp3)—C(sp), C(sp3)—C(sp2), and C(sp3)—C(sp3) bonds when allied with follow-up transformations.

Suggested Citation

  • Zhen-Hua Zhang & Xiao-Yang Dong & Xuan-Yi Du & Qiang-Shuai Gu & Zhong-Liang Li & Xin-Yuan Liu, 2019. "Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C(sp3)−H bonds with alkynes," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-13705-1
    DOI: 10.1038/s41467-019-13705-1
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    Cited by:

    1. Jianke Su & Yu Guo & Chengbo Li & Qiuling Song, 2024. "Difluorocarbene-induced [1,2]- and [2,3]-Stevens rearrangement of tertiary amines," Nature Communications, Nature, vol. 15(1), pages 1-10, December.

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