环丙烷骨架膦配体的研究展望  

Perspective for Phosphine Ligands with Cyclopropane Backbone

作　　者：张艳东 朱守非[1] Zhang Yandong;Zhu Shoufei(Frontiers Science Center for New Organic Matter,State Key Laboratory of Elemento-Organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071,China)

机构地区：[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

出　　处：《化学学报》2023年第7期777-783,共7页Acta Chimica Sinica

基　　金：国家重点研发计划(2021YFA1500200);国家自然科学基金(92256301,92156006,22221002,21971119);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;科学探索奖的资助。

摘　　要：按照配体类型划分,系统总结了已知环丙烷骨架含膦(包括单膦、双膦、膦-杂原子及三膦)配体及其在过渡金属催化中的应用.环丙烷具有成为优势膦配体骨架的潜力:一方面,环丙烷骨架具有刚性的平面结构,三个碳原子上的取代基具有联动关系;另一方面,环丙烷的结构拉大了其碳上取代基的键角,增大了这些取代基的几何结构可调性;此外,环丙烷的构筑方法多样而且有效,这为环丙烷膦配体的结构多样性合成提供了得天独厚的条件.然而,迄今以环丙烷为核心骨架的膦配体报道很少,其应用亦有待挖掘.希望能够引起研究者们对于环丙烷骨架含膦配体的重视,推动过渡金属催化领域的发展.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 appl

关 键 词：环丙烷骨架 膦配体 催化有机合成 活性 选择性 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]