Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (7): 777-783.DOI: 10.6023/A23040125 Previous Articles     Next Articles



张艳东, 朱守非*()   

  1. 南开大学 化学学院 元素有机化学国家重点实验室 有机新物质创造前沿科学中心 天津 300071
  • 投稿日期:2023-04-10 发布日期:2023-05-16
  • 作者简介:

    张艳东, 2015年本科毕业于三峡大学. 目前在南开大学化学学院攻读博士学位. 主要从事环丙烷骨架双膦配体铁系金属配合物催化的氢转移反应研究.

    朱守非, 南开大学化学学院教授. 1996~2005年在南开大学化学学院学习, 获得理学学士和理学博士学位; 2012~2013年在日本东京大学做博士后; 2005年至今在南开大学化学学院工作, 2013年晋升为教授. 长期从事催化有机合成化学研究, 重点研究了几类以氢转移为关键步骤的有机合成反应, 提出了“手性质子梭催化剂”概念, 发现了催化硼氢键插入新反应, 发展了多种新型负氢转移催化剂.

  • 基金资助:
    国家重点研发计划(2021YFA1500200); 国家自然科学基金(92256301); 国家自然科学基金(92156006); 国家自然科学基金(22221002); 国家自然科学基金(21971119); 教育部“111”引智计划(B06005); 物质绿色创造与制造海河实验室、中央高校基本科研业务费专项资金以及科学探索奖的资助

Perspective for Phosphine Ligands with Cyclopropane Backbone

Yandong Zhang, Shoufei Zhu()   

  1. Frontiers Science Center for New Organic Matter, State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
  • Received:2023-04-10 Published:2023-05-16
  • Contact: *E-mail:
  • About author:
    Dedicated to the 90th anniversary of Acta Chimica Sinica.
  • Supported by:
    National Key R&D Program(2021YFA1500200); National Natural Science Foundation of China(92256301); National Natural Science Foundation of China(92156006); National Natural Science Foundation of China(22221002); National Natural Science Foundation of China(21971119); “111” project(B06005); Ministry of Education of China, Haihe Laboratory of Sustainable Chemical Transformations, the Fundamental Research Funds for the Central Universities and Xplorer Prize

Throughout the history of transition-metal catalysis, almost every breakthrough is closely related to the development of ligands. Therefore, the history of transition-metal catalysis roughly parallels the development history of ligands. Therefore, ligand development lies in the heart of transition metal catalysis. Since the beginning of homogeneous catalysis, transition metals have been accompanied by phosphine ligands (Wilkinson's catalyst). Till now, phosphine ligands are one of the most widely used ligand types. There are several key factors for the popularity of phosphine ligands, among which the backbone of ligand plays a decisive role in supporting their stability, activity and selectivity. Many privileged phosphine ligands contain five- or six-membered rings in their core structures, possibly due to their ready-availability, low ring strain, and high stability. Seven- and above membered cyclic structures have flexible frameworks, many stable conformations, and are difficult to synthesize, making them unsuitable as ligand backbones. The cyclobutane structure has relatively strong ring strain, but its conformation can be flipped, and it is difficult to synthesize, making it inappropriate to be used as a ligand skeleton, too. As the smallest all-carbon ring, the three carbon atoms of cyclopropane are located in the same plane. Because of the unique electronic structure and rigidity of cyclopropane, changing a substituent on any one of the carbon atoms of the ring will affect the conformation of the substituents on the other two carbons. And cyclopropane structure is relatively simple to synthesize and modify, making it a promising ligand skeleton. However, it is surprising that phosphine ligands with cyclopropane as the core structure have been rarely studied so far, and their applications need to be further explored, too. Based on types of ligands, this perspective systematically summarizes reported phosphine-containing ligands (including monophosphines, diphosphines, phosphine-heteroatoms and triphosphines) with cyclopropane backbone, and their applications in transition metal catalysis. We hope to draw researchers' attention to the cyclopropane-based phosphine ligands and thus promote the development of transition metal catalysis.

Key words: cyclopropane skeleton, phosphine ligands, catalytic organic synthesis, activity, selectivity