Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States.
J Org Chem. 2020 Apr 3;85(7):5065-5072. doi: 10.1021/acs.joc.9b03465. Epub 2020 Mar 13.
Two complementary rational synthetic routes have been developed in order to synthesize hangman chlorins, which differ with regard to the order of the installation (pre- and post-formation of the chlorin macrocycle) and position of the xanthene backbone about the chlorin periphery. The versatility of the synthetic method is demonstrated with the preparation of ten new hangman chlorins bearing a xanthene backbone and a pendant carboxylic acid. Cyclic voltammograms of hangman chlorins exhibit a hangman effect derived from intermolecular proton transfer. This hangman effect is manifested in catalytic hydrogen evolution production.
已经开发出两种互补的合理合成路线来合成绞索叶绿素，这两种路线的区别在于叶绿素大环的安装顺序（形成前和形成后）以及呫吨骨架在叶绿素外围的位置。该合成方法的多功能性通过制备十个带有呫吨骨架和侧挂羧酸的新型绞索叶绿素得到了证明。绞索叶绿素的循环伏安曲线表现出源于分子间质子转移的绞索效应。这种绞索效应表现在催化析氢产物中。
