Surface-Controlled Mono/Diselective ortho C–H Bond Activation

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• 作者：Qing Li ; Biao Yang ; Haiping Lin ; Nabi Aghdassi ; Kangjian Miao ; Junjie Zhang ; Haiming Zhang ; Youyong Li ; Steffen Duhm ; Jian Fan ; Lifeng Chi
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：March 2, 2016
• 年：2016
• 卷：138
• 期：8
• 页码：2809-2814
• 全文大小：515K
• ISSN：1520-5126

文摘

One of the most charming and challenging topics in organic chemistry is the selective C–H bond activation. The difficulty arises not only from the relatively large bond-dissociation enthalpy, but also from the poor reaction selectivity. In this work, Au(111) and Ag(111) surfaces were used to address ortho C–H functionalization and ortho-ortho couplings of phenol derivatives. More importantly, the competition between dehydrogenation and deoxygenation drove the diversity of reaction pathways of phenols on surfaces, that is, diselective ortho C–H bond activation on Au(111) surfaces and monoselective ortho C–H bond activation on Ag(111) surfaces. The mechanism of this unprecedented phenomenon was extensively explored by scanning tunneling microscopy, density function theory, and X-ray photoelectron spectroscopy. Our findings provide new pathways for surface-assisted organic synthesis via the mono/diselective C–H bond activation.