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Regioselective Markovnikov hydrodifluoroalkylation of alkenes using difluoroenoxysilanes

Author

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  • Xiao-Si Hu

    (East China Normal University)

  • Jun-Xiong He

    (East China Normal University)

  • Su-Zhen Dong

    (East China Normal University)

  • Qiu-Hua Zhao

    (East China Normal University)

  • Jin-Sheng Yu

    (East China Normal University
    Hainan Normal University)

  • Jian Zhou

    (East China Normal University
    Shanghai Institute of Organic Chemistry, CAS)

Abstract

Alkene hydrodifluoroalkylation is a fruitful strategy for synthesizing difluoromethylated compounds that are interesting for developing new medicinal agents, agrochemicals, and advanced materials. Whereas the anti-Markovnikov hydrodifluoroalkylation to linear-type products is developed, employing radical-based processes, the Markovnikov synthesis of branched adducts remains unexplored. Herein, we describe acid-catalyzed processes involving carbocation intermediates as a promising strategy to secure the Markovnikov regioselectivity. Accordingly, the Markovnikov hydrodifluoroalkylation of mono-, di-, tri-, and tetrasubstituted alkenes using difluoroenoxysilanes, catalyzed by Mg(ClO4)2·6H2O, is achieved. This allows the diversity-oriented synthesis of α,α-difluoroketones with a quaternary or tertiary carbon at the β-position that are otherwise difficult to access. The method is applied to the modification of natural products and drug derivatives. The resulting α,α-difluorinated ketones could be converted to the corresponding α,α-difluorinated esters or alcohols, or organofluorine compounds featuring a CF2H or CF2CF2Ph moiety. Mechanistic studies support that Mg(ClO4)2·6H2O functions as a hidden Brønsted acid catalyst.

Suggested Citation

  • Xiao-Si Hu & Jun-Xiong He & Su-Zhen Dong & Qiu-Hua Zhao & Jin-Sheng Yu & Jian Zhou, 2020. "Regioselective Markovnikov hydrodifluoroalkylation of alkenes using difluoroenoxysilanes," Nature Communications, Nature, vol. 11(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-19387-4
    DOI: 10.1038/s41467-020-19387-4
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    Cited by:

    1. Linxuan Li & Xinyu Zhang & Yongquan Ning & Xiaolong Zhang & Binbin Liu & Zhansong Zhang & Paramasivam Sivaguru & Giuseppe Zanoni & Shuang Li & Edward A. Anderson & Xihe Bi, 2022. "Carbodefluorination of fluoroalkyl ketones via a carbene-initiated rearrangement strategy," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    2. Xuan Cheng & Quan Yin & Yi-Fei Cheng & Shao-Hua Wu & Xin-Chang Sun & De-Yi Kong & Qing-Hai Deng, 2024. "Practical and regioselective halonitrooxylation of olefins to access β-halonitrates," Nature Communications, Nature, vol. 15(1), pages 1-10, December.

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