9-氨基奎宁催化剂催化1-溴代硝基甲烷和亚苄基丙酮的共轭加成反应的理论研究

doi:10.7503/cjcu20140136

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (7): 1500.doi: 10.7503/cjcu20140136

9-氨基奎宁催化剂催化1-溴代硝基甲烷和亚苄基丙酮的共轭加成反应的理论研究

姜海洋, 冯伟, 孙艳伟, 齐乔芳, 田宏伟, 刘慧玲, 黄旭日()

吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130021

收稿日期:2014-02-24 出版日期:2014-07-10 发布日期:2019-08-01
作者简介:联系人简介: 黄旭日, 男, 博士, 教授, 博士生导师, 主要从事化学微观反应机理研究. E-mail: huangxr@jlu.edu.cn
基金资助:
国家“九七三”计划项目(批准号: 2012CB932800f)和国家自然科学基金(批准号: 21173097, 21373099, 21303067)资助

Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine^†

JIANG Haiyang, FENG Wei, SUN Yanwei, QI Qiaofang, TIAN Hongwei, LIU Huiling^*, HUANG Xuri^*()

State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Received:2014-02-24 Online:2014-07-10 Published:2019-08-01
Contact: LIU Huiling,HUANG Xuri E-mail:huangxr@jlu.edu.cn
Supported by:
Supported by State Key Development Program for Basic Research of China(No.2012CB932800f) and the National Natural Science Foundation of China(Nos.21173097, 21373099, 21303067)

摘要/Abstract

摘要：

通过密度泛函理论(DFT) B3LYP, M062X和从头算方法MP2, 给出了9-氨基奎宁作为有机催化剂和苯甲酸作为辅助催化剂催化1-溴代硝基甲烷与亚苄基丙酮的不对称共轭加成反应的详细反应机理. 反应过程主要包括3个阶段: (1) 亚胺离子中间体的形成; (2) 亚胺离子与1-溴代硝基甲烷的亲核加成; (3) 水解并伴随催化剂的还原. 计算结果不仅解释了苯甲酸加合物在亚胺离子形成过程中所起的重要作用, 而且提供了一般反应模型以理解这个共轭加成反应的反应机理和对映选择性.

关键词: 密度泛函理论, 从头算方法, 不对称共轭加成反应机理, 对映选择性, 9-氨基奎宁

Abstract:

Asymmetric conjugate addition of 1-bromonitromethane tobenzylidene acetone was catalyzed by 9-amino-9-deoxyepiquinine as organic catalyst and benzoic acid as co-catalyst. We had identified a detailed mechanism of the title reaction with density functional theory(B3LYP and M062X) and ab initio calculations(MP2). The reaction process includes three major stages: (1) the formation of an iminium ion intermediate; (2) the nucleophilic addition between the iminium and 1-bromonitromethane; (3) hydrolysis and recovery of catalyst. The calculated results not only explain benzoic acid as acidic additive plays an important role in the formation of the key reaction iminium intermediate, but also provide a general model to help explain the mechanism and enantioselectivity of the conjugate addition reaction.

Key words: Density functional theory, Ab initio calculation, Mechanism of asymmetric conjugate addition, Enantioselectivity, 9-Amino-9-deoxyepiquinine

中图分类号:

O641

TrendMD:

姜海洋, 冯伟, 孙艳伟, 齐乔芳, 田宏伟, 刘慧玲, 黄旭日. 9-氨基奎宁催化剂催化1-溴代硝基甲烷和亚苄基丙酮的共轭加成反应的理论研究. 高等学校化学学报, 2014, 35(7): 1500.

JIANG Haiyang, FENG Wei, SUN Yanwei, QI Qiaofang, TIAN Hongwei, LIU Huiling, HUANG Xuri. Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine^†. Chem. J. Chinese Universities, 2014, 35(7): 1500.

图/表 10

Fig.1 Mechanism A for the formation of the iminium intermediates[27]

Fig.2 Mechanism B for the formation of the iminium intermediates

Fig.3 Optimized geometries and selected geometric parameters for the formation of iminium intermediate Some hydrogen atoms of the catalyst not involved in reaction sites are omitted; distances are in nm.

Fig.4 Bond dissociation curves calculated via point-wise optimized method at the B3LYP/6-31+G(d,p) level of theory

Fig.5 Relative energy profile for the formation of iminium intermediate Values of ΔG are given in parentheses.

Fig.6 Optimized geometries and selected geometric parameters for the addition reaction etween iminium intermediate and 1-bromonitromethane

Fig.7 Optimized geometries and selected geometric parameters for the hydrolysis and regeneration of the catalyst Some hydrogen atoms not involved in reaction sites are omitted; distances are in nm.

Fig.8 Four pathways to the S or R enantiomers, respectively

Fig.9 Relative energy profiles for the addition reaction for the real reaction system Values of ΔE are given in parentheses and ΔG in brackets.

Fig.10 Relative energy profiles for the hydrolysis to obtain the final product for the real reaction system Values of ΔE are given in parentheses and ΔG in brackets.

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9-氨基奎宁催化剂催化1-溴代硝基甲烷和亚苄基丙酮的共轭加成反应的理论研究

Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine^†

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9-氨基奎宁催化剂催化1-溴代硝基甲烷和亚苄基丙酮的共轭加成反应的理论研究

Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine†

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PDF (PC)

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Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine^†