Unusual Two-Step Claisen-type Rearrangement Reaction under Physiological Conditions

CORC > 生态环境研究中心 > 中国科学院生态环境研究中心 > 环境化学与生态毒理学国家重点实验室

	Unusual Two-Step Claisen-type Rearrangement Reaction under Physiological Conditions
	Huang, Chun-Hua; Xu, Dan; Qin, Li; Li, Pei-Lin; Tang, Tian-Shu; Zhu, Ben-Zhan
刊名	JOURNAL OF ORGANIC CHEMISTRY
	2020-12-04
卷号	85 期号:23 页码:14945-14953
ISSN号	0022-3263
英文摘要	N-aryl hydroxamic acids, which are best known for their metal-chelating properties in chemical and biomedical research, have been found to markedly detoxify carcinogenic halogenated quinones. However, the exact chemical mechanism underlying such detoxication remains unclear. Here, we show that a very fast reaction took place between N-phenylbenzohydroxamic acid (N-PhBHA) and 2,5-dichloro-1,4-benzoquinone (DCBQ), forming an unexpected new carbon-carbon bonding phenyl-quinone product with high yield. In contrast, no reaction was observed with O-benzoyl N-PhBHA. Analogous results were observed for other N-aryl hydroxamic acids and halogenated quinones, which have an ortho-hydrogen adjacent to the reaction site (DCBQtype). Interestingly, no free radical intermediates could be detected by both ESR spin-trapping and radical-scavenging methods during the reaction process. Taken together, we proposed that nucleophilic substitution followed by an unusual two-step Claisen-type rearrangement reaction was responsible for the formation of a new C-C bonding compound and the detoxication reaction. This represents the first report of an unusually mild and facile two-step Claisen-type rearrangement, which could take place under normal physiological conditions.
内容类型	期刊论文
源URL	[http://ir.rcees.ac.cn/handle/311016/44852]
专题	生态环境研究中心_环境化学与生态毒理学国家重点实验室
推荐引用方式 GB/T 7714	Huang, Chun-Hua,Xu, Dan,Qin, Li,et al. Unusual Two-Step Claisen-type Rearrangement Reaction under Physiological Conditions[J]. JOURNAL OF ORGANIC CHEMISTRY,2020,85(23):14945-14953.
APA	Huang, Chun-Hua,Xu, Dan,Qin, Li,Li, Pei-Lin,Tang, Tian-Shu,&Zhu, Ben-Zhan.(2020).Unusual Two-Step Claisen-type Rearrangement Reaction under Physiological Conditions.JOURNAL OF ORGANIC CHEMISTRY,85(23),14945-14953.
MLA	Huang, Chun-Hua,et al."Unusual Two-Step Claisen-type Rearrangement Reaction under Physiological Conditions".JOURNAL OF ORGANIC CHEMISTRY 85.23(2020):14945-14953.