Selective Monofunctionalization Enabled by Reaction-History-Dependent Communication in Catalytic Rotaxanes.
Selective Monofunctionalization Enabled by Reaction-History-Dependent Communication in Catalytic Rotaxanes.
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DOI：
10.1002/anie.202006305
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发表时间：
2020-09-14
期刊：
影响因子：
--
通讯作者：
Schneebeli ST
中科院分区：
文献类型：
--
作者：
Rajappan SC;McCarthy DR;Campbell JP;Ferrell JB;Sharafi M;Ambrozaite O;Li J;Schneebeli ST
由于一旦第一官能团已经反应，就需要第二官能团选择性地调节其反应性，所以很难实现具有远距离但等活性官能团的底物的选择性单官能化。我们现在发现，机械互锁的催化环可以有效地调节轮烷中封端基团在~2 nm距离内的反应活性。我们的通讯机制是由独特的联锁设计实现的，一旦第一次反应发生，它就通过快速脱线有效地从底物上移除催化环。我们的方法不仅导致了一个罕见的选择性单官能化的例子，而且还产生了一个“分子IF函数”。总体而言，这篇研究文章中报道的结果提供了一种方法，使远程官能团以依赖于反应历史的方式相互通信，以创建最终可以在分子水平上执行逻辑操作的连接体。在催化环的帮助下，轮烷中遥远的末端现在可以以依赖于反应历史的方式相互交谈，催化环在末端之间自由穿梭。有了这个动态控制的信息传递机制，一端知道另一端是否已经反应，如果是，用什么试剂。接收到该信息的终端然后基于该信息调整其反应性。
Selective monofunctionalization of substrates with distant, yet equally-reactive functional groups is difficult to achieve, as it requires the second functional group to selectively modulate its reactivity once the first functional group has reacted. We now show that mechanically-interlocked catalytic rings can effectively regulate the reactivity of stoppering groups in rotaxanes over a distance of ~2 nm. Our mechanism of communication is enabled by a unique interlocked design, which effectively removes the catalytic rings from the substrates via fast dethreading, as soon as the first reaction has taken place. Our method not only led to a rare example of selective monofunctionalization, but also to a “molecular if function”. Overall, the results reported in this research article present a way to get distant functional groups to communicate with each other in a reaction-history-dependent manner to create linkers that can ultimately perform logical operations at the molecular level. Distant ends in rotaxanes can now talk to each other in a reaction history-dependent manner with the help of a catalytic ring, which shuttles freely between the ends. With this kinetically controlled information transfer mechanism, one end knows whether the other end has reacted, and if yes with what reagent. The end receiving this information then adjusts its reactivity based on this information.
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