Supramolecular Relay-Control of Organocatalysis with a Hemithioindigo-Based Molecular Motor,Journal of the American Chemical Society

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Supramolecular Relay-Control of Organocatalysis with a Hemithioindigo-Based Molecular Motor
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-10-28 , DOI: 10.1021/jacs.0c09519
Kerstin Grill ₁ , Henry Dube ₁

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Integration of individual molecular components such as molecular motors or switches into larger meta-functional systems represents a current challenge at the forefront of molecular machine research. Here we present a modular supramolecular approach to relay the photoinduced geometry changes of a hemithioindigo based molecular motor into catalytic efficiency of a chemical reaction. Using the intrinsic chemical nature of the motor for recognition of different hydrogen-bonding organocatalysts a greater than 10-fold modulation in binding affinity is achieved upon photoisomerization. This change in affinity is then translated effectively into control of catalytic competence of the organocatalysts without direct interference by the motor. As an example the organocatalysed Michael addition reaction between nitrostyrene and 3-methoxy-dimethyl aniline was modulated in situ by visible light irradiation. Thus, dynamic and reversible remote control of catalytic processes by the switching capacity of a hemithioindigo molecular motor is established in a multicomponent chemical system. The high intrinsic modularity of this approach presents further advantages, e.g., for easy tailoring of conditions or facile exchange of catalysts and reactions. These results represent a first stepping stone into integrated chemical networks regulated by molecular machines in a fully dynamic way.

中文翻译：

半硫靛基分子马达对有机催化的超分子继电器控制

将分子马达或开关等单个分子组件集成到更大的元功能系统中代表了当前分子机器研究前沿的挑战。在这里，我们提出了一种模块化超分子方法，将基于半硫靛的分子马达的光致几何变化转化为化学反应的催化效率。使用马达的内在化学性质来识别不同的氢键有机催化剂，在光异构化时实现了 10 倍以上的结合亲和力调制。这种亲和力的变化随后被有效地转化为对有机催化剂催化能力的控制，而不受电机的直接干扰。例如，硝基苯乙烯和 3-甲氧基-二甲基苯胺之间的有机催化迈克尔加成反应通过可见光照射原位调节。因此，在多组分化学系统中建立了通过半硫靛分子马达的开关能力对催化过程的动态和可逆远程控制。这种方法的高内在模块化表现出进一步的优势，例如，易于调整条件或催化剂和反应的容易交换。这些结果代表了进入由分子机器以完全动态方式调节的综合化学网络的第一步。在多组分化学系统中建立了通过半硫靛蓝分子马达的开关能力对催化过程的动态和可逆远程控制。这种方法的高内在模块化表现出进一步的优势，例如，易于调整条件或催化剂和反应的容易交换。这些结果代表了进入由分子机器以完全动态方式调节的综合化学网络的第一步。在多组分化学系统中建立了通过半硫靛蓝分子马达的开关能力对催化过程的动态和可逆远程控制。这种方法的高内在模块化表现出进一步的优势，例如，易于调整条件或催化剂和反应的容易交换。这些结果代表了进入由分子机器以完全动态方式调节的综合化学网络的第一步。

更新日期：2020-10-28

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