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题名: Rhodium-Catalyzed C-H Activation of Phenacyl Ammonium Salts Assisted by an Oxidizing C-N Bond: A Combination of Experimental and Theoretical Studies
作者: Yu, Songjie1;  Liu, Song2;  Lan, Yu2;  Wan, Boshun1;  Li, Xingwei1
刊名: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
发表日期: 2015-02-04
DOI: 10.1021/ja511796h
卷: 137, 期:4, 页:1623-1631
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Multidisciplinary
研究领域[WOS]: Chemistry
英文摘要: Rh(III)-catalyzed C-H activation assisted by an oxidizing directing group has evolved to a mild and redox-economic strategy for the construction of heterocycles. Despite the success, these coupling systems are currently limited to cleavage of an oxidizing N-O or N-N bond. Cleavage of an oxidizing C-N bond, which allows for complementary carbocycle synthesis, is unprecedented. In this article, alpha-ammonium acetophenones with an oxidizing C-N bond have been designed as substrates for Rh(III)-catalyzed C-H activation under redox-neutral conditions. The coupling with alpha-diazo esters afforded benzocyclopentanones, and the coupling with unactivated alkenes such as styrenes and aliphatic olefins gave ortho-olefinated acetophenoes. In both systems the reactions proceeded with a broad scope, high efficiency, and functional group tolerance. Moreover, efficient one-pot coupling of diazo esters has been realized starting from alpha-bromoacetophenones and triethylamine. The reaction mechanism for the coupling with diazo esters has been studied by a combination of experimental and theoretical methods. In particular, three distinct mechanistic pathways have been scrutinized by DFT studies, which revealed that the C-H activation occurs via a C-bound enolate-assisted concerted metalation-deprotonation mechanism and is rate-limiting. In subsequent C-C formation steps, the lowest energy pathway involves two rhodium carbene species as key intermediates.
关键词[WOS]: POLARIZABLE CONTINUUM MODEL ;  DIRECTING GROUP ;  INTERNAL OXIDANT ;  REGIOSELECTIVE SYNTHESIS ;  CARBENOID FUNCTIONALIZATION ;  RH(III)-CATALYZED SYNTHESIS ;  CONVERGENT SYNTHESIS ;  EFFICIENT SYNTHESIS ;  ORTHO-ALKENYLATION ;  ACID-DERIVATIVES
语种: 英语
WOS记录号: WOS:000349138600039
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/145951
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
2.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China

Recommended Citation:
Yu, Songjie,Liu, Song,Lan, Yu,et al. Rhodium-Catalyzed C-H Activation of Phenacyl Ammonium Salts Assisted by an Oxidizing C-N Bond: A Combination of Experimental and Theoretical Studies[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015,137(4):1623-1631.
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