Zhang Wei, Moore Jeffrey S
Department of Chemistry and Materials Science & Engineering, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801, USA.
Angew Chem Int Ed Engl. 2006 Jul 3;45(27):4416-39. doi: 10.1002/anie.200503988.
Shape-persistent arylene ethynylene macrocycles have attracted much attention in supramolecular chemistry and materials science because of their unique structures and novel properties. In this Review we describe recent examples of macrocycle synthesis by cross-coupling (Sonogashira: aryl acetylene macrocycle or Glaser: aryl diacetylene macrocycle) and dynamic covalent chemistry. The primary disadvantage of the coupling methods is the kinetically determined product distribution, since a significant portion of oligomers grow beyond the length of the cyclic targets ("overshooting"). Better results have been obtained recently by a dynamic covalent approach involving reversible metathesis reactions that afford macrocycles in one step. Mechanistic studies demonstrate that macrocycle formation is thermodynamically controlled by this route. Remaining synthetic challenges include the efficient preparation of site-specifically functionalized structures and larger, more complex two- and three-dimensional molecules.
形状持久的亚芳基乙炔大环化合物因其独特的结构和新颖的性质，在超分子化学和材料科学领域备受关注。在本综述中，我们描述了通过交叉偶联（Sonogashira反应：芳基乙炔大环或Glaser反应：芳基二乙炔大环）和动态共价化学合成大环化合物的近期实例。偶联方法的主要缺点是动力学决定产物分布，因为相当一部分低聚物的生长超过了环状目标物的长度（“过度延伸”）。最近，通过涉及可逆复分解反应的动态共价方法一步合成大环化合物，取得了更好的结果。机理研究表明此路线中环化反应是由热力学控制的。剩余的合成挑战包括高效制备位点特异性功能化结构以及更大、更复杂的二维和三维分子。
