Direct Synthesis of High-Valent Aryl-Cu(II) and Aryl-Cu(III) Compounds: Mechanistic Insight into Arene C-H Bond Metalation

doi:10.1021/ja412615h

CORC > 化学研究所 > 中国科学院化学研究所

	Direct Synthesis of High-Valent Aryl-Cu(II) and Aryl-Cu(III) Compounds: Mechanistic Insight into Arene C-H Bond Metalation
	Zhang, Hu 1,2; Yao, Bo 1,2; Zhao, Liang 1; Wang, De-Xian 2; Xu, Bo-Qing 1; Wang, Mei-Xiang 1
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2014-04-30
卷号	136 期号:17 页码:6326-6332
ISSN号	0002-7863
DOI	10.1021/ja412615h
英文摘要	Copper and its salts are abundant, inexpensive, and eco-friendly and have been used as the surrogates of noble metals to effect arene C H bond activation and transformations. Despite of the recent significant progress of the study, syntheses of high-valent arylcopper(II-III) compounds are still very rare and mechanisms of copper(II)-catalyzed reactions remain elusive. With the use of azacalix[1]arene[3]pyridines as a platform, a number of arylcopper(II) compounds were synthesized efficiently from the reaction of Cu(ClO4)(2) under ambient conditions. The resulting aryl Cu(II) compounds, which contain an unprecedented (substituted) phenyl Cu(II) sigma-bond, were stable under atmospheric conditions and can undergo facile oxidation reaction by free copper(II) ions or oxone to afford arylcopper(III) compounds in good yields. Both arylcopper(II) and arylcopper(III) compounds were characterized unambiguously by means of XRD, XPS, and NMR methods. Experimental evidence including reaction kinetics, LFER and KIE, and theoretical indicated that the Cu(ClO4)(2)-mediated arene C-H bond activation proceeds plausibly through an electrophilic aromatic metalation pathway. The synthesis of high-valent arylcopper compounds and the reaction mechanism reported here highlight the diversity and richness of organocopper chemistry.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000335369200035
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/50873]
专题	中国科学院化学研究所
通讯作者	Wang, Mei-Xiang
作者单位	1.Tsinghua Univ, Minist Educ, Key Lab Bioorgan Phosphorus Chem & Chem Biol, Beijing 100084, Peoples R China 2.Chinese Acad Sci, Inst Chem, CAS Key Lab Mol Recognit & Funct, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Zhang, Hu,Yao, Bo,Zhao, Liang,et al. Direct Synthesis of High-Valent Aryl-Cu(II) and Aryl-Cu(III) Compounds: Mechanistic Insight into Arene C-H Bond Metalation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2014,136(17):6326-6332.
APA	Zhang, Hu,Yao, Bo,Zhao, Liang,Wang, De-Xian,Xu, Bo-Qing,&Wang, Mei-Xiang.(2014).Direct Synthesis of High-Valent Aryl-Cu(II) and Aryl-Cu(III) Compounds: Mechanistic Insight into Arene C-H Bond Metalation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,136(17),6326-6332.
MLA	Zhang, Hu,et al."Direct Synthesis of High-Valent Aryl-Cu(II) and Aryl-Cu(III) Compounds: Mechanistic Insight into Arene C-H Bond Metalation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 136.17(2014):6326-6332.