Scholarlink

<p>Catalytic hydrogenation is essential in synthetic chemistry, with ongoing innovations aimed at enhancing the selectivity and efficiency of these reactions. The hydrogenation of multisubstituted allenes, however, presents a long-standing challenge due to the difficulty of controlling multiple selectivity factors simultaneously. Here we introduce a series of chiral pincer cobalt catalysts featuring multiple metal–ligand cooperative functionalities. These catalysts feature an ‘N–H’ moiety as an outer-sphere binding site and an N-heterocycle group as a hemilabile basic site, enabling the use of structurally diverse tridentate ligands for selective hydrogenation of functionalized allenes. This design liberates a coordination site for H<sub>2</sub> activation and enhances selectivity control through the structural tuning of the N-heterocycle group. The catalysts exhibit exceptional chemo-, regio-, enantio- and <i>Z</i>/<i>E</i>-selectivities, along with broad functional group tolerance, enabling access to all possible semihydrogenation products of multisubstituted allenes. Mechanistic studies uncover a distinctive redox-neutral Co(I) catalytic cycle that facilitates heterolytic cleavage of H<sub>2</sub>, assisted by the basic N-heterocycle on the ligand.</p><p></p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Tunable cobalt-catalysed hydrogenation of allenes enabled by multiple metal–ligand cooperative functionalities

  • 期刊论文

  • 发表日期：

    2025年9月26日

查看全文
  • Xianle Rong,
  • Yunjuan Ren,
  • Yongshun Chen,
  • Chongyao Li,
  • Jie Wang,
  • Zhaoqiang Chen,
  • Lizhi Tao,
  • Zhihong Wei,
  • Shengming Ma,
  • Qiang Liu

摘要

Catalytic hydrogenation is essential in synthetic chemistry, with ongoing innovations aimed at enhancing the selectivity and efficiency of these reactions. The hydrogenation of multisubstituted allenes, however, presents a long-standing challenge due to the difficulty of controlling multiple selectivity factors simultaneously. Here we introduce a series of chiral pincer cobalt catalysts featuring multiple metal–ligand cooperative functionalities. These catalysts feature an ‘N–H’ moiety as an outer-sphere binding site and an N-heterocycle group as a hemilabile basic site, enabling the use of structurally diverse tridentate ligands for selective hydrogenation of functionalized allenes. This design liberates a coordination site for H2 activation and enhances selectivity control through the structural tuning of the N-heterocycle group. The catalysts exhibit exceptional chemo-, regio-, enantio- and Z/E-selectivities, along with broad functional group tolerance, enabling access to all possible semihydrogenation products of multisubstituted allenes. Mechanistic studies uncover a distinctive redox-neutral Co(I) catalytic cycle that facilitates heterolytic cleavage of H2, assisted by the basic N-heterocycle on the ligand.