Citation: Bian Rongjian, Bao Xiaoguang. Computational Insights into the Mechanism of Pd (0) and Ben-zoic Acid Co-Catalyzed Hydroamination of Internal Alkynes[J]. Chinese Journal of Organic Chemistry, ;2017, 37(1): 190-195. doi: 10.6023/cjoc201607005 shu

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

Corresponding author: Bao Xiaoguang, xgbao@suda.edu.cn
Received Date: 4 July 2016
Revised Date: 28 August 2016

Fund Project: the National Natural Science Foundation of China 21302133

Figures(5)

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.
- Pd catalysis,
- carboxylic acid,
- DFT,
- hydroamination,
- reaction mechanism
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