Substituent Effects on the Carboxylation Step of Allyllic Substrates: A Density Functional Theory Study
Substituent Effects on the Carboxylation Step of Allyllic Substrates: A Density Functional Theory Study
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DOI：
10.1002/slct.202300831
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发表时间：
2023-05
期刊：
影响因子：
2.1
通讯作者：
Chengyu Yao;Deguang Liu;Zheyuan Xu;Haizhu Yu;Jing Shi
中科院分区：
文献类型：
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作者：
Chengyu Yao;Deguang Liu;Zheyuan Xu;Haizhu Yu;Jing Shi
Ni（0/I）催化烯丙醇直接羧基化反应是制备β， γ‐不饱和羧酸的有效途径，羧基化反应是一个关键的基本步骤。利用密度泛函理论（DFT）计算，我们研究了取代基如何影响羧基化过程。在Ni(0)的情况下，羧基化过程的能垒相对较低，这可以通过给电子基团（烯丙基- α - C）有效地降低。其他远端部位的影响较小。虽然有一定的阈值，但空间效应对该反应的影响是微不足道的。利用预中间体的NPA、Fukui函数和Wiberg键指数进行多元线性回归拟合羧基化反应的能垒。结果表明，通过预中间体的性质参数可以很容易地预测羧基化反应的能垒，省去了复杂的过渡态计算。
Ni(0/I) catalysed direct carboxylation of allyl alcohols represents an effective way to create β, γ‐unsaturated carboxylic acids, with the carboxylation to be a crucial elementary step. Using density functional theory (DFT) calculations, we investigated how substituents affected the carboxylation process. The energy barrier of the carboxylation process is relatively low in the case of Ni(0), which can be efficiently lowered down by electron‐donating group (at allyl‐α‐C). Other distal sites have less of an impact. The steric effect on this reaction is insignificant, although there is a certain threshold. Multiple linear regression was taken to fit the energy barrier of the carboxylation step using the NPA, Fukui function, and Wiberg bond index of the pre‐intermediate The results showed that the energy barrier of the carboxylation step can be easily predicted by the property parameter of the pre‐intermediate, eliminating the complex transition state calculation.