Imine or Enamine? Insights and Predictive Guidelines from the Electronic Effect of Substituents in H-Bonded Salicylimines.
Imine or Enamine? Insights and Predictive Guidelines from the Electronic Effect of Substituents in H-Bonded Salicylimines.
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亚胺还是烯胺？
DOI：
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发表时间：
2020
影响因子：
3.6
通讯作者：
J. Palacios
中科院分区：
文献类型：
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作者：
R. Martínez;E. Matamoros;P. Cintas;J. Palacios
亚胺和烯胺键装饰着许多试剂、催化剂和有机材料的骨架。然而，要随意分离单个互变异构体是困难的，因为即使在固态下，动态平衡也很容易发生，并且对电子和空间效应很敏感，包括π-共轭和氢键。在这里，以水杨醛和Tris生成的席夫碱为模型，在一组线性自由能关系(LFER)中，我们揭示了如何控制亚胺或烯胺的形成，并提供了一个全面的框架来捕捉这一预测的结构基础。这项工作突出了定制设计在生产具有理想功能的化合物的过程中的潜力。
Imine and enamine bonds decorate the skeleton of numerous reagents, catalysts, and organic materials. However, it is difficult to isolate at will a single tautomer, as dynamic equilibria occur easily, even in the solid state, and are sensitive to electronic and steric effect, including π-conjugation and H-bonding. Here, using as model Schiff bases generated from salicylaldehydes and TRIS in a set of linear free energy relationships (LFER), we disclose how the formation of either imines or enamines can be controlled and provide a comprehensive framework that captures the structural underpinning of this prediction. This work highlights the potentiality of tailor-made designs en route to compounds with desirable functionality.