Citation: AN Xiao-Ying, HE Rong-Xing, HUANG Cheng, LI Ming. Mechanism of AuCl₃-Catalyzed Synthesis of Highly Substituted Furans Based on 2-(1-Alkynyl)-2-alken-1-ones[J]. Acta Physico-Chimica Sinica, ;2011, 27(03): 577-583. doi: 10.3866/PKU.WHXB20110338 shu

Mechanism of AuCl₃-Catalyzed Synthesis of Highly Substituted Furans Based on 2-(1-Alkynyl)-2-alken-1-ones

1.
College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. China

Received Date: 17 October 2010
Available Online: 21 February 2011
Fund Project: 教育部科学技术重点项目(104263)资助 (104263)

We investigated the mechanism of the AuCl₃-catalyzed synthesis of highly substituted furans from 2-(1-alkynyl)-2-alken-1-ones with nucleophiles using the density functional theory (DFT) with B3LYP function, and obtained the optimal pathway. The rate-determining step of the cyclization is H-migration from the hydroxy group to a ligand Cl of AuCl₃ with a 49.3 kJ·mol^-1 energy barrier. The calculated results show that the ligand Cl of AuCl₃ plays an important role in the reaction, which stabilizes the catalyst and is also directly involved in the reaction. The active energy of proton transfer decreases from 71.5 to 49.3 kJ·mol^-1 by assisting the proton transfer. In addition, the reason why HBF₄ cannot catalyze the cyclization of 2-(1-alkynyl)-2-alken-1-ones is also discussed in this work. The theoretical results are consistent with the experimental observations.
- AuCl₃,
- Mechanism,
- Density functional theory,
- Furan,
- Ligand
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Mechanism of AuCl3-Catalyzed Synthesis of Highly Substituted Furans Based on 2-(1-Alkynyl)-2-alken-1-ones

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通讯作者: 陈斌, bchen63@163.com

Mechanism of AuCl₃-Catalyzed Synthesis of Highly Substituted Furans Based on 2-(1-Alkynyl)-2-alken-1-ones