A Density Functional Theory Study of the Mechanism of Cu(II)-Catalyzed Synthesis of Pyrido[1,2-a]benzimidazoles

doi:10.6023/cjoc201501034

Chin. J. Org. Chem. ›› 2015, Vol. 35 ›› Issue (8): 1726-1732.DOI: 10.6023/cjoc201501034 Previous Articles Next Articles

ARTICLE

Cu(II)催化合成吡啶并[1,2-a]苯并咪唑的密度泛函理论研究

杜丽娟, 吴彩虹, 顾红红, 李娟

暨南大学化学系广州 510632

收稿日期:2015-02-06 修回日期:2015-03-14 发布日期:2015-04-10
通讯作者: 李娟 E-mail:tchjli@jnu.edu.cn
基金资助:
国家自然科学基金(No. 21103072)和中央高校基本科研业务费专项资金(No. 21615405)资助项目.

A Density Functional Theory Study of the Mechanism of Cu(II)-Catalyzed Synthesis of Pyrido[1,2-a]benzimidazoles

Du Lijuan, Wu Caihong, Gu Honghong, Li Juan

Department of Chemistry, Jinan University, Guangzhou 510632

Received:2015-02-06 Revised:2015-03-14 Published:2015-04-10
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21103072) and the Fundamental Research Funds for the Central Universities (No. 21615405).

1. A Density Functional Theory Study of the Mechanism of Cu(II)-Catalyzed Synthesis of Pyrido[1,2-a]benzimidazoles.PDF(439KB)

Abstract

The reaction mechanism of Cu(II)-catalyzed synthesis of pyrido[1,2-a]benzimidazoles was theoretically investigated with the aid of density functional theory calculations (DFT) at the B3LYP level. Five possible mechanisms for the synthesis were proposed: (1) C—H-bond-breaking step preceding deprotonation of imino group, and finally C—N bond formation (Pathway a), (2) deprotonation of imino group preceding C—H-bond-breaking step, and finally C—N bond formation (Pathway b), (3) C—H-bond-breaking as the first step, then C—N bond formation preceding deprotonation of imino group (Pathway c), (4) the anti-imino-cupration mechanism (Pathway d), (5) the Friedel-Crafts alkylation mechanism (Pathway e). The calculation results indicate that the most favorable pathway involves C—H bond breaking by concerted metalation/deprotonation (CMD), followed by N—H deprotonation along the triplet state and C—N bond formation (Pathway a). A clear understanding of the reaction mechanism of pyrido[1,2-a]benzimidazoles formation should lead to more efficient synthetic strategies.

Key words: density functional theory(DFT), Cu(II)-Catalyzed, C—N cross coupling, mechanistic study

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Du Lijuan, Wu Caihong, Gu Honghong, Li Juan. A Density Functional Theory Study of the Mechanism of Cu(II)-Catalyzed Synthesis of Pyrido[1,2-a]benzimidazoles[J]. Chin. J. Org. Chem., 2015, 35(8): 1726-1732.

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Cu(II)催化合成吡啶并[1,2-a]苯并咪唑的密度泛函理论研究

A Density Functional Theory Study of the Mechanism of Cu(II)-Catalyzed Synthesis of Pyrido[1,2-a]benzimidazoles

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