铜催化内炔的硅羧基化反应机理及区域选择性的密度泛函理论研究

引用本文: 赵义, 周晋, 刘会, 禚淑萍. 铜催化内炔的硅羧基化反应机理及区域选择性的密度泛函理论研究[J]. 物理化学学报, 2015, 31(10): 1864-1871. doi: 10.3866/PKU.WHXB201508281 shu

Citation: ZHAO Yi, ZHOU Jin, LIU Hui, ZHUO Shu-Ping. Reaction Mechanism and the Regioselectivity of Cu-Catalyzed Silacarboxylation of Internal Alkynes: a Density Functional Theory Study[J]. Acta Physico-Chimica Sinica, 2015, 31(10): 1864-1871. doi: 10.3866/PKU.WHXB201508281 shu

铜催化内炔的硅羧基化反应机理及区域选择性的密度泛函理论研究

基金项目:
国家自然科学基金(51302156, 21302057) (51302156, 21302057)

山东省自然科学基金联合专项(ZR2014BL012)资助项目 (ZR2014BL012)

摘要:

用CO₂作为原料, 在过渡金属催化下生成新的碳碳键是很重要的. 在这类反应中, 杂原子官能团和CO₂同时与不饱和的底物被催化生成高功能化的羧酸衍生物已经越来越受到人们的关注. 本文采用密度泛函理论(DFT)方法, 研究了金属铜催化剂催化内炔的硅羧基化反应机理. 根据炔烃上甲基和苯环两个取代基的相对位置, 提出了两条反应路径(path I: 甲基和path II: 苯环). 计算结果表明炔烃插入Cu－Si键既是速率决速步骤也是区域选择决速步骤. 在path I中, 炔烃插入Cu－Si键的自由能为112.8 kJ·mol^-1, 而在path II中为127.6kJ·mol^-1. 显然, path I比path II在动力学上更有利, 这与实验上两条路径对应产物的产率97: 3是一致的. 分析表明区域选择性是由炔烃取代基甲基和苯环的电子效应决定的.

关键词:

English

Reaction Mechanism and the Regioselectivity of Cu-Catalyzed Silacarboxylation of Internal Alkynes: a Density Functional Theory Study

1.
School of Chemical Engineering, Shandong University of Technology, Zibo 255049, Shandong Province, P. R. China
Received Date: 01 July 2015
Available Online: 10 October 2015
Fund Project:
国家自然科学基金(51302156, 21302057)

山东省自然科学基金联合专项(ZR2014BL012)资助项目

Abstract:

Transition metal-catalyzed carbon-carbon bond formation utilizing CO₂ is of great importance. The heteroatom functionality and CO₂ are simultaneously and catalytically incorporated into unsaturated substrates to form highly functionalized carboxylic acid derivatives. Here, density functional theory (DFT) is used to study the reaction mechanisms of the Cu-catalyzed silacarboxylation of internal alkynes. Two possible paths were proposed depending on the relative positions of the substituents (path I: methyl and path II: phenyl). The calculations reveal that the initial alkyne insertion into the Cu―Si bond determined both the rate and the selectivity. In path I, the calculated free energy barrier for alkyne insertion is 112.8 kJ·mol^-1, while that in path II is 127.6 kJ·mol^-1. Thus, path I is more kinetically favorable than path II, which is consistent with the experimentally observed product ratio of 97 : 3. Our analysis revealed that the electronic effects of the alkyne substituents dominated the observed regioselectivity.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

铜催化内炔的硅羧基化反应机理及区域选择性的密度泛函理论研究

English

Reaction Mechanism and the Regioselectivity of Cu-Catalyzed Silacarboxylation of Internal Alkynes: a Density Functional Theory Study

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

铜催化内炔的硅羧基化反应机理及区域选择性的密度泛函理论研究

English

Reaction Mechanism and the Regioselectivity of Cu-Catalyzed Silacarboxylation of Internal Alkynes: a Density Functional Theory Study

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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