Nickel-Catalyzed Ring-Opening of Benzofurans for the Divergent Synthesis of ortho-Functionalized Phenol Derivatives

作者：Lu, Changhui; Lin, Yueping; Wang, Minyan^*; Zhou, Jiaming; Wang, Shuo; Jiang, Huanfeng; Kang, Kai; Huang, Liangbin^*

来源：ACS Catalysis, 2023, 13(4): 2432-2442.

DOI：10.1021/acscatal.2c04442

• benzofuran
• nickel catalysis
• ring-opening transformation
• C
• O bond activation
• cascade reactions

The ring-opening reaction of benzofuran is a highly desirable, yet underdeveloped transformation for the construction of valuable phenol derivatives. Herein, we report a nickel-catalyzed ring-opening transformation of benzofuran with silanes, giving ortho-alkene-, branched/linear alkyl silane-, and alkenyl silanesubstituted phenol derivatives selectively. Control experiments and DFT calculations supported Ni-H insertion and beta-O elimination to achieve the formal C-O bond activation of benzofuran but not through the direct oxidative addition of nickel (0) into the C-O bond of benzofurans. Further regioselective hydrosilylation or dehydrogenative silylation occurs via Ni(I)-H or Ni(I)-[Si] intermediates to form ortho-branched/linear alkyl silane- or alkenyl silane-substituted phenol derivatives.

• 单位
  南京大学