A Theoretical Study on Pd-catalyzed, Friedel-Crafts Intermolecular Acylation: Does Generated In Situ Aroyl Triflate Act as A Reactive Electrophile to Functionalize C-H Bond of Arenes?
A Theoretical Study on Pd-catalyzed, Friedel-Crafts Intermolecular Acylation: Does Generated In Situ Aroyl Triflate Act as A Reactive Electrophile to Functionalize C-H Bond of Arenes?
复制标题
Pd 催化的 Friedel-Crafts 分子间酰化的理论研究：原位生成的芳酰基三氟甲磺酸酯能否作为反应性亲电子试剂使芳烃的 C-H 键功能化？
DOI：
10.3390/catal9020141
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发表时间：
2019
期刊：
影响因子：
3.9
通讯作者：
Li Yanrong
中科院分区：
文献类型：
--
作者：
Chang Rong;Tian Ye;Li Niu;Bai Jin;Yan Huimin;Yang Wenjing;Guo Zhen;Li Yanrong
用密度泛函理论研究了钯催化芳烃分子间Friedel-Crafts酰化反应的机理。计算结果表明，该转化过程包括C-I键氧化加成、CO插入、还原消除和C-H键功能化等几个关键步骤。在这些步骤中，发现最后一步是速率决定步骤，并且与其他所得对应物相比，用强亲电芳酰基三氟甲磺酸酯更容易发生。此外，我们的计算提供了一个基本原理的实验结果，简单的钯盐表现出上级催化能力相比，膦配位的钯催化剂。
The mechanism of Pd-catalyzed, Friedel-Crafts intermolecular acylation of arenes to ketones was comprehensively investigated by using DFT calculations. The calculated results revealed that this transformation was composed of several key steps: C-I bond oxidative addition, CO insertion, reductive elimination and C-H bond functionalization. Of these steps, the last was found to be the rate-determining step, and it occurred much more easily with strongly electrophilic aroyl triflate compared to other resultant counterparts. In addition, our calculation provides a rationale for experimental findings that simple Pd salts exhibit superior catalytic abilities compared to phosphine-ligated Pd catalysts.