Synthesis of a Bis-macrocycle Containing Two Back-to-Back Rigidly Connected 1,10-Phenanthroline Units as a Central Core and its Incorporation in a Handcuff-Like Catenane
作者:Julien Frey、Tomáš Kraus、Valérie Heitz、Jean-Pierre Sauvage
DOI:10.1002/chem.200700671
日期:2007.9.17
performing a double ring-closing metathesis reaction. This final cyclisation reaction is high yielding and affords the desired catenane consisting of a bis-macrocycle of which the two cyclic units are threaded by a large ring. The compound has been fully characterised by classical techniques. Electronic spectroscopy and electrochemical measurements suggest that the two copper complex subunits do not interact
制备了包含两个背对背连接的1,10-菲咯啉螯合物的双宏环。合成策略涉及制备由1,10-菲咯啉-5,6-二酮片段并入30元环组成的单环前体。这种重要的中间体是通过两种不同的途径制备的,两种策略均依赖于使用缩酮作为1,2-二酮保护基。在还原剂(Na(2)S(2)O(4))存在下,两个大环二酮分子与两个当量的氨(过量使用)之间的四组分缩合反应导致所需的二环产量高。最直接的合成路线允许从1,10-菲咯啉分七个步骤制备双宏环,总收率为14%。使用现成的“ 可以定量获得双螺纹物质,其中双大环的每个环都被“分子串”穿过。这些片段带有末端烯丙基基团,其用于通过进行双闭环易位反应来制备最终的链烷。该最终的环化反应是高产率的,并提供所需的由双大环组成的链烷烃,该双大环的两个环单元被大环连接。该化合物已通过经典技术充分表征。电子光谱和电化学测量表明,尽管两个金属中心之间的桥联配体具有芳族性质,但两个铜配合物亚基