Computational Insights into the Mechanism of Pd(0) and Ben-zoic Acid Co-Catalyzed Hydroamination of Internal Alkynes

doi:10.6023/cjoc201607005

Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (1): 190-195.DOI: 10.6023/cjoc201607005 Previous Articles Next Articles

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零价钯和苯甲酸共催化内炔烃氢胺化反应机理的理论研究

卞荣剑, 鲍晓光

苏州大学材料与化学化工学部苏州 215123

收稿日期:2016-07-04 修回日期:2016-08-28 发布日期:2016-09-01
通讯作者: 鲍晓光 E-mail:xgbao@suda.edu.cn
基金资助:
国家自然科学基金（No. 21302133）资助项目.

Computational Insights into the Mechanism of Pd(0) and Ben-zoic Acid Co-Catalyzed Hydroamination of Internal Alkynes

Bian Rongjian, Bao Xiaoguang

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123

Received:2016-07-04 Revised:2016-08-28 Published:2016-09-01
Supported by:
Project supported by the National Natural Science Foundation of China(No. 21302133).

Computational studies were carried out to investigate the detailed mechanism of Pd(0) and benzoic acid co-catalyzed hydroamination of internal alkynes.In the presence of the benzoic acid,the formation of a hydridopalladium intermediate via the oxidative addition(OA) of the O-H bond of benzoic acid into the Pd(0) complex center might not be a favorable reaction pathway to start the reaction.Instead,after the coordination of benzoic acid with the Pd(0)-alkyne complex,a proton transfer process from the acid to carbon of alkyne is found to be a favorable pathway,leading to the alkenyl(PhCOO) Pd(Ⅱ) intermediate.Next,the resulting alkenyl(PhCOO) Pd(Ⅱ) species would produce phenylallene intermediate via a β-H elimination step assisted by the formed benzoate anion.Subsequently,the benzoic acid might undergo a second proton step to the phenylallene intermediate to produce the π-allylpalladium species.Finally,the amine substrate could undergo a nucleophilic addition to the terminal carbon of the π-allylpalladium species to produce the hydroamination product.

Key words: Pd catalysis, carboxylic acid, DFT, hydroamination, reaction mechanism

Cite this article

Bian Rongjian, Bao Xiaoguang. Computational Insights into the Mechanism of Pd(0) and Ben-zoic Acid Co-Catalyzed Hydroamination of Internal Alkynes[J]. Chin. J. Org. Chem., 2017, 37(1): 190-195.

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[30] We also investigated the possibility of amine attack to the π-allylpalladium species from the other side to produce the hydroamination product. The located transition state(TS10), however, is 35.5 kJ/mol higher in energy than TS6, suggesting a disfavored pathway(see Figure S3).

零价钯和苯甲酸共催化内炔烃氢胺化反应机理的理论研究

Computational Insights into the Mechanism of Pd(0) and Ben-zoic Acid Co-Catalyzed Hydroamination of Internal Alkynes

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