Distribution of Spin Density on Phenoxyl Radicals Affects the Selectivity of Aerobic Oxygenation of Phenols

doi:10.1021/acs.inorgchem.9b02422

CORC > 上海应用物理研究所 > 中国科学院上海应用物理研究所 > 中科院上海应用物理研究所2011-2017年

	Distribution of Spin Density on Phenoxyl Radicals Affects the Selectivity of Aerobic Oxygenation of Phenols
	Wang, YT ; Guan, J ; Mei, BB ; Fan, MT ; Lu, R ; Du, RF ; Chen, KZ ; Yao, J ; Jiang, Z ; Li, HR
刊名	INORGANIC CHEMISTRY
	2020
卷号	59 期号:6 页码:3562-3569
关键词	OXIDATIVE POLYMERIZATION COPPER(II) COMPLEXES SUBSTITUTED PHENOLS CATALYZED OXIDATION MAGNETIC-RESONANCE MOLECULAR-OXYGEN 2,3,6-TRIMETHYLPHENOL TRIMETHYL-1,4-BENZOQUINONE REACTIVITY CHLORIDE
ISSN号	0020-1669
DOI	10.1021/acs.inorgchem.9b02422
文献子类	期刊论文
英文摘要	Phenoxyl radical was generally suggested as the intermediate during copper-catalyzed aerobic oxygenation of phenols. However, the substrate-dependent selectivity has not been well interpreted, due to insufficient characterization of the radical intermediate under reaction conditions. When studying the CuCl-LiCl-catalyzed aerobic phenol oxidation, we obtained EPR spectra of phenoxyl radicals generated by oxidizing phenols with the preactivated catalyst. Upon correlation to the selectivity of benzoquinone, the hyperfine coupling constant of para-site proton (a(H,) (para)) was found to be better than the Hammett constant. The catalysis mechanism was studied based on EPR detection and the reaction results of phenoxyl radicals under N-2 or O-2 atmosphere. It appeared that the chemoselectivity depended on the attack of activated dioxygen on phenoxyl radicals, and the activation of dioxygen by [CunCln+1](-) (n = 1, 2, 3) was suggested substrate-dependent selectivity contributed to predicting the chemo-selectivity in as the rate-determining step. Understanding of the the aerobic oxidation of phenols.
语种	英语
内容类型	期刊论文
源URL	[http://ir.sinap.ac.cn/handle/331007/32802]
专题	上海应用物理研究所_中科院上海应用物理研究所2011-2017年
作者单位	1.Zhejiang Univ, State Key Lab Chem Engn, Coll Chem & Biol Engn, Hangzhou 310027, Peoples R China 2.Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China 3.Zhejiang Univ, Dept Chem, ZJU NHU United R&D Ctr, Coll Chem & Biol Engn, Hangzhou 310027, Peoples R China
推荐引用方式 GB/T 7714	Wang, YT,Guan, J,Mei, BB,et al. Distribution of Spin Density on Phenoxyl Radicals Affects the Selectivity of Aerobic Oxygenation of Phenols[J]. INORGANIC CHEMISTRY,2020,59(6):3562-3569.
APA	Wang, YT.,Guan, J.,Mei, BB.,Fan, MT.,Lu, R.,...&Li, HR.(2020).Distribution of Spin Density on Phenoxyl Radicals Affects the Selectivity of Aerobic Oxygenation of Phenols.INORGANIC CHEMISTRY,59(6),3562-3569.
MLA	Wang, YT,et al."Distribution of Spin Density on Phenoxyl Radicals Affects the Selectivity of Aerobic Oxygenation of Phenols".INORGANIC CHEMISTRY 59.6(2020):3562-3569.