Mechanisms of Csp2–H functionalization of aldehydes with triplet O2 catalyzed by NHPI: A density functional theory investigation,Journal of Physical Organic Chemistry

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Mechanisms of Csp2–H functionalization of aldehydes with triplet O2 catalyzed by NHPI: A density functional theory investigation
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2020-07-27 , DOI: 10.1002/poc.4112
Zhe‐Peng Deng ₁ , Da‐Gang Zhou ₂

Affiliation

The mechanisms of Csp²–H activation of aldehydes to yield carboxylic acids catalyzed by NHPI have been investigated with M06‐2X‐D3/ma‐def2‐TZVP method and basis set in the Universal Solvation Model Based on Solute Electron Density (SMD). The computational results suggest that the activation of NHPI, rather than aldehydes, would be finished by triplet O₂ with lower energy barrier. The obtained radicals PINO and HOO˙ could help to achieve this Csp²–H activation of aldehydes, then triplet O₂ would continue to react with generated intermediate to obtain Criegee intermediate radical; the following H‐shift reactions happened to produce Criegee intermediate; finally, SN2 reaction would help to yield the final product carboxylic acid. Meanwhile, the obtained carboxylic acid radical captures one proton to yield carboxylic acid. The localized orbital locator (LOL) isosurfaces of pi orbitals, and electron spin density isosurface graphs could reveal the single electron transfer process. The results would provide valuable insights into these types of interactions and related ones.

中文翻译：

NHPI催化三重态O2对Csp2-H醛官能化的机理：密度泛函理论研究

用M06-2X-D3 / ma-def2-TZVP方法研究了Csp ² -H活化醛类化合物以NHPI催化生成羧酸的机理，并在基于溶质电子密度（SMD）的通用溶剂化模型中设定了基础。计算结果表明，NHPI而不是醛的活化将通过具有较低能垒的三重态O ₂完成。获得的自由基PINO和HOO˙可以帮助实现醛的Csp ² -H活化，然后使三重态O ₂活化。将继续与产生的中间体反应以获得克里基中间体自由基；随后发生的H移反应产生了Criegee中间体; 最后，SN2反应将有助于产生最终产物羧酸。同时，获得的羧酸基捕获一个质子以产生羧酸。π轨道的局部轨道定位器（LOL）等值面和电子自旋密度等值面图可以揭示单电子转移过程。结果将提供对这些类型的交互和相关交互的有价值的见解。

更新日期：2020-07-27

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