Adaptive Behavior of Dynamic Orthoester Cryptands.
Adaptive Behavior of Dynamic Orthoester Cryptands.
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DOI：
10.1002/anie.201609855
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发表时间：
2017-01
影响因子：
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通讯作者：
Oleksandr Shyshov;R. Brachvogel;Tobias Bachmann;R. Srikantharajah;D. Segets;F. Hampel;R. Puchta;
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文献类型：
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作者：
Oleksandr Shyshov;R. Brachvogel;Tobias Bachmann;R. Srikantharajah;D. Segets;F. Hampel;R. Puchta;
将动态共价键整合到大环中已经成为研究非共价相互作用和鉴定有效的主客体对的一个非常成功的策略。虽然许多研究都集中在大环化合物和大笼对各种客体的动态响应上，但穴状配体的相应组成动态化学仍然未被探索。这里报道的是，基于原酸酯桥头的穴状配体为实验提供了一个优雅的入口，在该实验中，金属离子从竞争子组分的动态混合物中选择其优选的宿主。在这样的动态混合物中，碱金属离子Li+，Na+，K+，Rb+，和Cs+表现出明显的偏好形成的穴状配体的某些尺寸和供体数量，并通过DFT计算合理化的选择。报道了手性原酸酯穴状化合物的首次自组装，并对立体异构体作为亚组分的应用进行了初步研究。
The integration of dynamic covalent bonds into macrocycles has been a tremendously successful strategy for investigating noncovalent interactions and identifying effective host-guest pairs. While numerous studies have focused on the dynamic responses of macrocycles and larger cages to various guests, the corresponding constitutionally dynamic chemistry of cryptands remains unexplored. Reported here is that cryptands based on orthoester bridgeheads offer an elegant entry to experiments in which a metal ion selects its preferred host from a dynamic mixture of competing subcomponents. In such dynamic mixtures, the alkali metal ions Li+ , Na+ , K+ , Rb+ , and Cs+ exhibit pronounced preferences for the formation of cryptands of certain sizes and donor numbers, and the selection is rationalized by DFT calculations. Reported is also the first self-assembly of a chiral orthoester cryptate and a preliminary study on the use of stereoisomers as subcomponents.