Rad Nazar, Sashuk Volodymyr
Institute of Physical Chemistry, Polish Academy of Sciences Kasprzaka 44/52 01-224 Warsaw Poland
Chem Sci. 2022 Oct 11;13(42):12440-12444. doi: 10.1039/d2sc02077g. eCollection 2022 Nov 2.
Competitive inhibition can be overcome by increasing the amount of catalyst in the reaction mixture. Here we present a pseudorotaxane system that circumvents this rule. A merocyanine inhibitor linked with the substrate obstructs the binding of the macrocyclic catalyst at the electrophilic reaction site preventing catalysis. Under UV light merocyanine is converted to the spiropyran form, losing its inhibition properties, thereby allowing the catalyst to bind the reaction center and promote the reaction. Moreover, when more than one nucleophile is present in the reaction mixture, the pseudorotaxane can scavenge a selected nucleophile and change the final product ratio. This work is a step forward in the development of new types of regulation in catalytic systems with remote control.
竞争性抑制作用可通过增加反应混合物中催化剂的量来克服。在此，我们展示了一种规避此规则的准轮烷体系。与底物相连的部花青抑制剂会阻碍大环催化剂在亲电反应位点的结合，从而阻止催化作用。在紫外光下，部花青会转化为螺吡喃形式，失去其抑制特性，从而使催化剂能够结合反应中心并促进反应。此外，当反应混合物中存在不止一种亲核试剂时，准轮烷可以清除选定的亲核试剂并改变最终产物的比例。这项工作是在远程控制催化体系新型调控开发方面向前迈出的一步。
