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Catalytic enantioconvergent coupling of secondary and tertiary electrophiles with olefins

Author

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  • Zhaobin Wang

    (California Institute of Technology)

  • Haolin Yin

    (California Institute of Technology)

  • Gregory C. Fu

    (California Institute of Technology)

Abstract

Carbon–carbon bonds, including those between sp3-hybridized carbon atoms (alkyl–alkyl bonds), typically comprise much of the framework of organic molecules. In the case of sp3-hybridized carbon, the carbon can be stereogenic and the particular stereochemistry can have implications for structure and function1–3. As a consequence, the development of methods that simultaneously construct alkyl–alkyl bonds and control stereochemistry is important, although challenging. Here we describe a strategy for enantioselective alkyl–alkyl bond formation, in which a racemic alkyl electrophile is coupled with an olefin in the presence of a hydrosilane, rather than via a traditional electrophile–nucleophile cross-coupling, through the action of a chiral nickel catalyst. We demonstrate that families of racemic alkyl halides—including secondary and tertiary electrophiles, which have not previously been shown to be suitable for enantioconvergent coupling with alkyl metal nucleophiles—cross-couple with olefins with good enantioselectivity and yield under very mild reaction conditions. Given the ready availability of olefins, our approach opens the door to developing more general methods for enantioconvergent alkyl–alkyl coupling.

Suggested Citation

  • Zhaobin Wang & Haolin Yin & Gregory C. Fu, 2018. "Catalytic enantioconvergent coupling of secondary and tertiary electrophiles with olefins," Nature, Nature, vol. 563(7731), pages 379-383, November.
  • Handle: RePEc:nat:nature:v:563:y:2018:i:7731:d:10.1038_s41586-018-0669-y
    DOI: 10.1038/s41586-018-0669-y
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    Citations

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    Cited by:

    1. Xiao-Xu Wang & Yuan-Tai Xu & Zhi-Lin Zhang & Xi Lu & Yao Fu, 2022. "NiH-catalysed proximal-selective hydroalkylation of unactivated alkenes and the ligand effects on regioselectivity," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    2. Xiaotao Zhu & Wujun Jian & Meirong Huang & Daliang Li & Yajun Li & Xinhao Zhang & Hongli Bao, 2021. "Asymmetric radical carboesterification of dienes," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    3. Yue Wang & Suping Zhang & Ke Zeng & Pengli Zhang & Xiaorong Song & Tie-Gen Chen & Guoqin Xia, 2024. "Deoxygenative radical cross-coupling of C(sp3)−O/C(sp3)−H bonds promoted by hydrogen-bond interaction," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    4. Qian Gao & Wei-Cheng Xu & Xuan Nie & Kang-Jie Bian & Hong-Rui Yuan & Wen Zhang & Bing-Bing Wu & Xi-Sheng Wang, 2024. "Regio‐ and enantioselective nickel-alkyl catalyzed hydroalkylation of alkynes," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    5. Wen-Tao Zhao & Jian-Xin Zhang & Bi-Hong Chen & Wei Shu, 2023. "Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides," Nature Communications, Nature, vol. 14(1), pages 1-7, December.
    6. Xiaoyang Li & Yufei Cao & Kai Luo & Lin Zhang & Yunxiu Bai & Jiarong Xiong & Richard N. Zare & Jun Ge, 2022. "Cooperative catalysis by a single-atom enzyme-metal complex," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    7. Daning Zeng & Zihao Liu & Guoce Huang & You Wang & Shaolin Zhu, 2024. "Regio-, stereo-, and enantioselective ipso- and migratory defluorinative olefin cross-coupling to access highly functionalized monofluoroalkenes," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    8. Jiangtao Ren & Zheng Sun & Shuang Zhao & Jinyuan Huang & Yukun Wang & Cheng Zhang & Jinhai Huang & Chenhao Zhang & Ruipu Zhang & Zhihan Zhang & Xu Ji & Zhihui Shao, 2024. "Enantioselective synthesis of chiral α,α-dialkyl indoles and related azoles by cobalt-catalyzed hydroalkylation and regioselectivity switch," Nature Communications, Nature, vol. 15(1), pages 1-14, December.

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