High-Yielding Flow Synthesis of a Macrocyclic Molecular Hinge.
High-Yielding Flow Synthesis of a Macrocyclic Molecular Hinge.
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DOI：
10.1021/jacs.1c02891
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发表时间：
2021-05-19
影响因子：
15
通讯作者：
Slater AG
中科院分区：
文献类型：
--
作者：
Jones CD;Kershaw Cook LJ;Marquez-Gamez D;Luzyanin KV;Steed JW;Slater AG
许多分子机器都是由具有明确运动能力的模块化组件构建的，例如轴和轮子。铰链是特别有用的，因为它们提供了简单和明显的构象变化所需的最小柔性。具有多个稳定构象的化合物是常见的，但分子铰链几乎完全通过二面角旋转而不是真正的铰链状夹紧机制来操作。理想的分子铰链将更好地再现铰链装置（例如门和镊子）的行为，同时保持可溶性、可扩展性和合成通用性。在这里，我们描述了两个异构体的大环与钳状开放和封闭的几何形状，结晶为单独的多晶型物，但在溶液中自由相互转换。一个不寻常的一锅加成环化反应是用来生产的大环化合物在一个多克规模从廉价的试剂，没有超分子模板或高稀释条件。利用NMR动力学研究和在线质谱的机理信息，我们开发了一种连续流动合成，最大转化率为85-93%，单一异构体的选择性超过80%。大环的特点是空间保护的客人，包括反应性物种，如氟离子的空隙，因此可以作为化学惰性铰链的自适应超分子受体和柔性多孔材料。
Many molecular machines are built from modular components with well-defined motile capabilities, such as axles and wheels. Hinges are particularly useful, as they provide the minimum flexibility needed for a simple and pronounced conformational change. Compounds with multiple stable conformers are common, but molecular hinges almost exclusively operate via dihedral rotations rather than truly hinge-like clamping mechanisms. An ideal molecular hinge would better reproduce the behavior of hinged devices, such as gates and tweezers, while remaining soluble, scalable, and synthetically versatile. Herein, we describe two isomeric macrocycles with clamp-like open and closed geometries, which crystallize as separate polymorphs but interconvert freely in solution. An unusual one-pot addition cyclization reaction was used to produce the macrocycles on a multigram scale from inexpensive reagents, without supramolecular templating or high-dilution conditions. Using mechanistic information from NMR kinetic studies and at-line mass spectrometry, we developed a semicontinuous flow synthesis with maximum conversions of 85–93% and over 80% selectivity for a single isomer. The macrocycles feature voids that are sterically protected from guests, including reactive species such as fluoride ions, and could therefore serve as chemically inert hinges for adaptive supramolecular receptors and flexible porous materials.
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影响因子：
3.2
作者：
Chen Y;Sun X;Wu N;Li J;Jin S;Zhong Y;Liu Z;Rogachev A;Chong HS
通讯作者：
Chong HS
影响因子：
21.8
作者：
Diaz, Diego B.;Appavoo, Solomon D.;Yudin, Andrei K.
通讯作者：
Yudin, Andrei K.
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
1.8
作者：
Ghosh, Kumaresh;Sarkar, Avik Ranjan;Patra, Amarendra
通讯作者：
Patra, Amarendra
影响因子：
2.1
作者：
Greenland, Barnaby W.;Burattini, Stefano;Colquhoun, Howard M.
通讯作者：
Colquhoun, Howard M.