Synergistic topological and supramolecular control of Diels-Alder reactivity based on a tunable self-complexing host-guest molecular switch
Synergistic topological and supramolecular control of Diels-Alder reactivity based on a tunable self-complexing host-guest molecular switch
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DOI：
10.1002/chem.202302300
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发表时间：
2024-01-10
影响因子：
4.3
通讯作者：
Woisel，Patrice
中科院分区：
文献类型：
--
作者：
Ribeiro，Cedric;Cariello，Michele;Woisel，Patrice
区室化和结合引发的构象变化调节着生命物质中的许多代谢过程。在这里，我们协同结合了这两个生物相关的过程，以调整合成的自络合主客体分子开关CBPQT 4 +-Fu的Diels-桤木（DA）反应性，该开关由共价连接到缺电子的环双（百草枯-对亚苯基）四氯化物（CBPQT 4+，4Cl−）主体的富电子呋喃单元组成。这种设计允许CBPQT 4 +-Fu在水中有效地分隔其宿主腔内的呋喃环，从而保护其免受马来酰亚胺的DA反应。值得注意的是，在加入更强结合分子萘衍生物作为竞争客体时，自复合的CBPQT 4 +-岩藻聚糖通过分子内解复合发生构象变化，在加入化学调节剂时触发DA反应。值得注意的是，将客体连接到热响应性低临界溶解温度（LCST）共聚物调节剂在加热和冷却反应介质超过和低于共聚物的浊点温度时根据命令控制DA反应，这代表了在升高温度时反应性降低的罕见实例。总而言之，这项工作开辟了新的途径，结合拓扑和超分子控制反应性的合成结构，使控制反应性通过分子调节剂，甚至温和的温度变化。
Compartmentalization and binding‐triggered conformational change regulate many metabolic processes in living matter. Here, we have synergistically combined these two biorelevant processes to tune the Diels‐Alder (DA) reactivity of a synthetic self‐complexing host‐guest molecular switchCBPQT4+‐Fu, consisting of an electron‐rich furan unit covalently attached to the electron‐deficient cyclobis(paraquat‐p‐phenylene) tetrachloride (CBPQT4+,4Cl−) host. This design allowsCBPQT4+‐Futo efficiently compartmentalize the furan ring inside its host cavity in water, thereby protecting it from the DA reaction with maleimide. Remarkably, the self‐complexedCBPQT4+‐Fucan undergo a conformational change through intramolecular decomplexation upon the addition of a stronger binding molecular naphthalene derivative as a competitive guest, triggering the DA reaction upon addition of a chemical regulator. Remarkably, connecting the guest to a thermoresponsive lower critical solution temperature (LCST) copolymer regulator controls the DA reaction on command upon heating and cooling the reaction media beyond and below the cloud point temperature of the copolymer, representing a rare example of decreased reactivity upon increasing temperature. Altogether, this work opens up new avenues towards combined topological and supramolecular control over reactivity in synthetic constructs, enabling control over reactivity through molecular regulators or even mild temperature variations.