Syntheses of three-dimensional catenanes under kinetic control.
Syntheses of three-dimensional catenanes under kinetic control.
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DOI：
10.1073/pnas.2118573119
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发表时间：
2022-03-22
影响因子：
11.1
通讯作者：
Stoddart JF
中科院分区：
文献类型：
--
作者：
Wu Y;Guo QH;Qiu Y;Weber JA;Young RM;Bancroft L;Jiao Y;Chen H;Song B;Liu W;Feng Y;Zhao X;Li X;Zhang L;Chen XY;Li H;Wasielewski MR;Stoddart JF
在过去的几十年中，有效的方法的发展，创造机械联锁分子（MIMs），如索烃和轮烷，不仅奠定了人工分子机器（AMM）的设计和合成的基础，但也开辟了新的研究机会，在多个学科，从当代化学到材料科学。在这项研究中，我们描述了一个suitane为基础的战略建设的三维（3D）catenanes，一个子集的MIM是远远不容易。与基于金属配位和动态共价化学的合成方法一起，这种方法使我们更接近于实现3D索烃的常规合成。尽管包含两个环形组分的索烃可以通过模板化大量制备，但具有笼形组分的三维（3D）索烃的制备仍处于起步阶段。在这里，我们报告的设计和合成的两个三维索烃的序列SN2反应在一锅。所得到的三重机械联锁分子在溶液和固体状态下的充分表征。机制研究表明，一套[3]烷，其中包含一个三重对称的笼组成的西装和三溴组成的机构，是在高温下形成。这种suit[3]ane被确定为选择性形成两种不代表热力学最小值的3D索烃的关键反应中间体。我们预见未来，这种特殊的合成策略指导合理的设计和生产的机械联锁分子动力学控制。
During the past decades, the development of efficient methodologies for the creation of mechanically interlocked molecules (MIMs), such as catenanes and rotaxanes, has not only laid the foundation for the design and syntheses of artificial molecular machines (AMMs) but also opened up new research opportunities in multiple disciplines, ranging from contemporary chemistry to materials science. In this study, we describe a suitane-based strategy for the construction of three-dimensional (3D) catenanes, a subset of MIMs that are far from easy to make. Together with synthetic methodologies based on the metal coordination and dynamic covalent chemistry, this approach brings us one step closer to realizing routine syntheses of 3D catenanes. Although catenanes comprising two ring-shaped components can be made in large quantities by templation, the preparation of three-dimensional (3D) catenanes with cage-shaped components is still in its infancy. Here, we report the design and syntheses of two 3D catenanes by a sequence of SN2 reactions in one pot. The resulting triply mechanically interlocked molecules were fully characterized in both the solution and solid states. Mechanistic studies have revealed that a suit[3]ane, which contains a threefold symmetric cage component as the suit and a tribromide component as the body, is formed at elevated temperatures. This suit[3]ane was identified as the key reactive intermediate for the selective formation of the two 3D catenanes which do not represent thermodynamic minima. We foresee a future in which this particular synthetic strategy guides the rational design and production of mechanically interlocked molecules under kinetic control.
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DOI：
10.1002/anie.201411619
发表时间：
2015-05-18
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Gil-Ramírez G;Leigh DA;Stephens AJ
通讯作者：
Stephens AJ
影响因子：
16.6
作者：
Fukuda, Morihiko;Sekiya, Ryo;Kuroda, Reiko
通讯作者：
Kuroda, Reiko
影响因子：
15
作者：
Cheng, Liwei;Liang, Chengyu;Wang, Shuao
通讯作者：
Wang, Shuao
影响因子：
15
作者：
Chen, Xiao-Yang;Shen, Dengke;Stoddart, J. Fraser
通讯作者：
Stoddart, J. Fraser
影响因子：
56.9
作者：
Chichak, KS;Cantrill, SJ;Stoddart, JF
通讯作者：
Stoddart, JF