Strain and stereoelectronics in cycloalkyne click chemistry
Strain and stereoelectronics in cycloalkyne click chemistry
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DOI：
10.1016/j.mencom.2019.05.001
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发表时间：
2019-05-01
影响因子：
1.9
通讯作者：
Alabugin, Igor V.
中科院分区：
文献类型：
--
作者：
Harris, Trevor;Alabugin, Igor V.
由于对环炔在无金属点击化学中的广泛兴趣，我们提出了一篇重点综述，总结了当前环炔结构和电子修饰的方法。我们说明了反应物不稳定和过渡态稳定的结合如何导致设计出更具反应性的环炔，但矛盾的是，这些环炔的张力较小。我们讨论了环炔中环应变的概念，并表明增加的环应变并不总是等于增加的点击反应性。我们总结了可用于增强环炔点击反应性的直接和远程电子效应，并展示了过渡态稳定立体电子效应对于环炔点击试剂的合理设计至关重要。
Due to the broad interest to cycloalkynes in metal-free click chemistry, we present a focused review summarizing current approaches to structural and electronic modifications of cycloalkynes. We illustrate how the combination of reactant destabilization and transition state stabilization can lead to the design of more reactive cycloalkynes that are, paradoxically, less strained. We discuss the concept of ring strain in cycloalkynes and show that increased ring strain does not always equate to increased click reactivity. We summarize direct and remote electronic effects that can be used to enhance click reactivity in cycloalkynes and show how inclusion of transition state stabilizing stereoelectronic effects is essential for the rational design of the cycloalkyne click reagents.