La Manna Pellegrino, De Rosa Margherita, Talotta Carmen, Rescifina Antonio, Floresta Giuseppe, Soriente Annunziata, Gaeta Carmine, Neri Placido
Laboratory of Supramolecular Chemistry, Dipartimento di Chimica e Biologia "A. Zambelli", Università di Salerno, Via Giovanni Paolo II, 132, 84084, Fisciano (Salerno), Italy.
Dipartimento di Scienze del Farmaco, Università di Catania, viale Andrea Doria, 6, 95125, Catania, Italy.
Angew Chem Int Ed Engl. 2020 Jan 7;59(2):811-818. doi: 10.1002/anie.201909865. Epub 2019 Nov 27.
The principle of amplified halogen bonding (XB) in a small space is exploited as a catalytic tool for the activation of an XB acceptor substrate in a nanoconfined environment. The inner cavity of the resorcinarene capsule has been equipped with an XB catalyst bearing an ammonium unit acting as a Trojan horse to drive the catalyst inside the capsule. In the presence of a specific XB catalyst, the capsule is able to catalyze a Michael reaction between N-methylpyrrole and methyl vinyl ketone. In the bulk medium in absence of the resorcinarene capsule, the XB catalyst is catalytically ineffective. Quantum-mechanical investigations highlight that the Michael reaction proceeds through the activation of the carbonyl group by synergistically enhanced halogen/hydrogen-bonding interactions and takes place in an open pentameric capsule.
在小空间内放大的卤键（XB）原理被用作一种催化工具，用于在纳米受限环境中活化XB受体底物。间苯二酚芳烃胶囊的内腔配备了一种带有铵单元的XB催化剂，该铵单元充当特洛伊木马，将催化剂驱动到胶囊内部。在特定XB催化剂存在下，该胶囊能够催化N-甲基吡咯与甲基乙烯基酮之间的迈克尔反应。在没有间苯二酚芳烃胶囊的本体介质中，XB催化剂没有催化活性。量子力学研究表明，迈克尔反应通过协同增强的卤键/氢键相互作用对羰基的活化而进行，并且发生在开放的五聚体胶囊中。
