刚性大环分子的合成:动力学及热力学方法之比较

基于刚性大环分子的独特结构和新颖性能,它们在超分子化学及材料科学领域已引起了广泛关注.侧重介绍一些近期用动态共价化学(dynamic covalent chemistry)方法合成大环分子的研究工作,及其和传统动力学控制的交叉耦合(cross - coupling)方法的比较.耦合方法的主要缺点在于共价键的形成不可逆,产品分布由动力学控制,由此导致大量长于(overshooting)目标大环分子的副产物生成.然而采用可逆复分解反应(metathesis reaction)的动态化学方法可以使大环化合物的合成更加高效.目前,该领域所面临的挑战包括高效制备位置专一性的大环化合物以及更加复杂的二维和三维的分子结构.

Synthesis of shape - persistent macrocycles: kinectic vs thermodynamic approach

Shape - persistent macrocycles have attracted much attention in supramolecular chemistry and materials science because of their unique structures and novel properties. In this minireview the au-thor describe some recent examples of macrocycle synthesis by dynamic covalent chemistry and compare such thermodynamic approach with conventional, kinetically controlled cross - coupling approach. 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. Remaining synthetic challenges include the efficient preparation of site - specifically functionalized structures and larger, more complex two - and three - dimensional molecules.