Mechanistic Investigation of Au(III)-Catalyzed Cycloisomerizations of N-Propargylcarboxamides

NWIPB OpenIR

	Mechanistic Investigation of Au(III)-Catalyzed Cycloisomerizations of N-Propargylcarboxamides
	Liu, Yuxia; Liu, Peng; Ling, Baoping; Chen, Guang; Chen, Tao; Li, Yulin; Bi, Siwei; Zhang, Dongju
	2019
发表期刊	EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
卷号	2019 期号:40
摘要	DFT calculations of the AuCl3-catalyzed cycloisomerization of N-(propargyl)benzamide (1) have been conducted to reveal the detailed mechanism resulting in the bioactive 2,5-disubstituted oxazole. A viable mechanism is established, featuring the co-catalysis of the oxazoline-AuCl3 adduct. An oxazoline intermediate is afforded firstly by AuCl3 coordination with 1, 5-exo-dig-cyclization, stepwise 1-assisted protodeauration and coordination exchange. Once formed, the oxazoline species would replace 1 to assist the protodeauration, generating the oxazoline-AuCl3 adduct. In the last stage, significantly different from the simple deprotonation followed by protodeauration reported previously, the exo-cyclic C atom of the oxazoline accepts the adjacent allyl H atom of the oxazoline-AuCl3 to produce a zwitterionic intermediate, from which the allyl H atom of oxazoline fragment transfers to the allyl C atom of the adduct moiety, affording the final oxazole product and regenerating the oxazoline-AuCl3. The present theoretical study provides new insight into the mechanism of the unusual cycloisomerization reaction.
关键词	AuCl3 catalysis Cycloisomerization N-(propargyl)benzamide Mechanism Density functional calculations
文献类型	期刊论文
条目标识符	http://210.75.249.4/handle/363003/59684
专题	中国科学院西北高原生物研究所
推荐引用方式 GB/T 7714	Liu, Yuxia,Liu, Peng,Ling, Baoping,et al. Mechanistic Investigation of Au(III)-Catalyzed Cycloisomerizations of N-Propargylcarboxamides[J]. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY,2019,2019(40).
APA	Liu, Yuxia.,Liu, Peng.,Ling, Baoping.,Chen, Guang.,Chen, Tao.,...&Zhang, Dongju.(2019).Mechanistic Investigation of Au(III)-Catalyzed Cycloisomerizations of N-Propargylcarboxamides.EUROPEAN JOURNAL OF ORGANIC CHEMISTRY,2019(40).
MLA	Liu, Yuxia,et al."Mechanistic Investigation of Au(III)-Catalyzed Cycloisomerizations of N-Propargylcarboxamides".EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2019.40(2019).