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NiH-catalysed proximal-selective hydroalkylation of unactivated alkenes and the ligand effects on regioselectivity

Author

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  • Xiao-Xu Wang

    (University of Science and Technology of China)

  • Yuan-Tai Xu

    (University of Science and Technology of China)

  • Zhi-Lin Zhang

    (University of Science and Technology of China)

  • Xi Lu

    (University of Science and Technology of China)

  • Yao Fu

    (University of Science and Technology of China
    Hefei Comprehensive National Science Center)

Abstract

Alkene hydrocarbonation reactions have been developed to supplement traditional electrophile-nucleophile cross-coupling reactions. The branch-selective hydroalkylation method applied to a broad range of unactivated alkenes remains challenging. Herein, we report a NiH-catalysed proximal-selective hydroalkylation of unactivated alkenes to access β- or γ-branched alkyl carboxylic acids and β-, γ- or δ-branched alkyl amines. A broad range of alkyl iodides and bromides with different functional groups can be installed with excellent regiocontrol and availability for site-selective late-stage functionalization of biorelevant molecules. Under modified reaction conditions with NiCl2(PPh3)2 as the catalyst, migratory hydroalkylation takes place to provide β- (rather than γ-) branched products. The keys to success are the use of aminoquinoline and picolinamide as suitable directing groups and combined experimental and computational studies of ligand effects on the regioselectivity and detailed reaction mechanisms.

Suggested Citation

  • 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.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-29554-4
    DOI: 10.1038/s41467-022-29554-4
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    References listed on IDEAS

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    1. Jia-Wang Wang & Yan Li & Wan Nie & Zhe Chang & Zi-An Yu & Yi-Fan Zhao & Xi Lu & Yao Fu, 2021. "Catalytic asymmetric reductive hydroalkylation of enamides and enecarbamates to chiral aliphatic amines," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    2. Sarah Z. Tasker & Eric A. Standley & Timothy F. Jamison, 2014. "Recent advances in homogeneous nickel catalysis," Nature, Nature, vol. 509(7500), pages 299-309, May.
    3. Xianxiao Chen & Weidong Rao & Tao Yang & Ming Joo Koh, 2020. "Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation," Nature Communications, Nature, vol. 11(1), pages 1-9, December.
    4. Xi Lu & Bin Xiao & Zhenqi Zhang & Tianjun Gong & Wei Su & Jun Yi & Yao Fu & Lei Liu, 2016. "Practical carbon–carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation," Nature Communications, Nature, vol. 7(1), pages 1-8, September.
    5. Sarah Z. Tasker & Eric A. Standley & Timothy F. Jamison, 2014. "Erratum: Recent advances in homogeneous nickel catalysis," Nature, Nature, vol. 510(7503), pages 176-176, June.
    6. Honggui Lv & Huiying Kang & Biying Zhou & Xiaosong Xue & Keary M. Engle & Dongbing Zhao, 2019. "Nickel-catalyzed intermolecular oxidative Heck arylation driven by transfer hydrogenation," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    7. 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.
    8. Shan Wang & Jian-Xin Zhang & Tian-Yi Zhang & Huan Meng & Bi-Hong Chen & Wei Shu, 2021. "Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
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