Selective hydration of asymmetric internal aryl alkynes without directing groups to alpha-aryl ketones over Cu-based catalyst

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	Selective hydration of asymmetric internal aryl alkynes without directing groups to alpha-aryl ketones over Cu-based catalyst
	Mei, Qingqing; Liu, Huizhen; Hou, Minqiang; Liu, Hangyu; Han, Buxing
刊名	NEW JOURNAL OF CHEMISTRY
	2017-07-21
卷号	41 期号:14 页码:6290-6295
英文摘要	Hydration of internal aryl alkynes to provide aryl carbonyl compounds is a class of important reactions and has been widely investigated. However, the hydration of asymmetric internal aryl alkynes without directing groups usually gives an aryl ketone or a mixture of aryl ketone and alpha-aryl ketone. High regioselectivity to alpha-aryl ketone is a great challenge and has not been reported. Herein, we found that CuBr and p-fluoroaniline had an excellent synergistic effect in catalyzing the hydration of internal aryl alkynes without directing groups to alpha-aryl ketones with regioselectivity up to more than 90%, which is much greater than those reported. The reaction mechanism was proposed, and the reason for the high selectivity was clarified by a combination of density functional theory (DFT) calculation, condensed dual descriptor (CDD) study, and experimental results. It was demonstrated that the formations of alpha-aryl ketone and aryl ketone were promoted by different catalytic active species, CuBr and CuBr[pfluoroaniline], respectively. CuBr enlarged the difference of electron population on the two triple-bond carbon atoms, resulting in alpha-aryl ketones as the main products.
语种	英语
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/38980]
专题	化学研究所_胶体、界面与化学热力学实验室
作者单位	Chinese Acad Sci, Inst Chem, CAS Key Lab Colloid & Interface & Thermodynam, BNLMS, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Mei, Qingqing,Liu, Huizhen,Hou, Minqiang,et al. Selective hydration of asymmetric internal aryl alkynes without directing groups to alpha-aryl ketones over Cu-based catalyst[J]. NEW JOURNAL OF CHEMISTRY,2017,41(14):6290-6295.
APA	Mei, Qingqing,Liu, Huizhen,Hou, Minqiang,Liu, Hangyu,&Han, Buxing.(2017).Selective hydration of asymmetric internal aryl alkynes without directing groups to alpha-aryl ketones over Cu-based catalyst.NEW JOURNAL OF CHEMISTRY,41(14),6290-6295.
MLA	Mei, Qingqing,et al."Selective hydration of asymmetric internal aryl alkynes without directing groups to alpha-aryl ketones over Cu-based catalyst".NEW JOURNAL OF CHEMISTRY 41.14(2017):6290-6295.