<p>Herein, we report a novel, visible-light-induced approach for the selective construction of both <i>gem</i>-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived <i>N</i>-alkoxyphthalimides as alkyl radical precursors. This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor (EDA) complex-mediated hydroalkylation process. By modulating the reaction conditions, the desired products were selectively obtained with excellent chemo-selectivity and in high yields. The protocol accommodates a wide variety of substrates, including primary, secondary, and tertiary alcohols, as well as diverse α-trifluoromethyl styrenes, and is applicable to late-stage functionalization of natural products and bioactive molecules.</p>

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Chemodivergent defluorinative alkylation and hydroalkylation of α-trifluoromethyl alkenes via Eosin Y catalysis and EDA photochemistry

  • Tianshuai Zhu,
  • Xinyu Xie,
  • Yue Zhang,
  • Hua-Wei Liu,
  • Jing-Jing Zhang,
  • Lijun Tang,
  • Weiwei Fang,
  • Zhen Chen

摘要

Herein, we report a novel, visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors. This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor (EDA) complex-mediated hydroalkylation process. By modulating the reaction conditions, the desired products were selectively obtained with excellent chemo-selectivity and in high yields. The protocol accommodates a wide variety of substrates, including primary, secondary, and tertiary alcohols, as well as diverse α-trifluoromethyl styrenes, and is applicable to late-stage functionalization of natural products and bioactive molecules.