中国科学院大连化学物理研究所机构知识库
Advanced  
DICP OpenIR  > 中国科学院大连化学物理研究所  > 期刊论文
学科主题: 物理化学
题名: Homogenous Pd-Catalyzed Asymmetric Hydrogenation of Unprotected Indoles: Scope and Mechanistic Studies
作者: Duan, Ying1;  Li, Lu2;  Chen, Mu-Wang1;  Yu, Chang-Bin1;  Fan, Hong-Jun1;  Zhou, Yong-Gui1
通讯作者: 樊红军 ;  周永贵
刊名: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
发表日期: 2014-05-28
DOI: 10.1021/ja502020b
卷: 136, 期:21, 页:7688-7700
收录类别: SCI ;  IC
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: An efficient palladium-catalyzed asymmetric hydrogenation of a variety of unprotected indoles has been developed that gives up to 98% ee using a strong Bronsted acid as the activator. This methodology was applied in the facile synthesis of biologically active products containing a chiral indoline skeleton. The mechanism of Pd-catalyzed asymmetric hydrogenation was investigated as well. Isotope-labeling reactions and ESI-HRMS proved that an iminium salt formed by protonation of the C=C bond of indoles was the significant intermediate in this reaction. The important proposed active catalytic Pd-H species was observed with H-1 NMR spectroscopy. It was found that proton exchange between the Pd-H active species and solvent trifluoroethanol (TFE) did not occur, although this proton exchange had been previously observed between metal hydrides and alcoholic solvents. Density functional theory calculations were also carried out to give further insight into the mechanism of Pd-catalyzed asymmetric hydrogenation of indoles. This combination of experimental and theoretical studies suggests that Pd-catalyzed hydrogenation goes through a stepwise outer-sphere and ionic hydrogenation mechanism. The activation of hydrogen gas is a heterolytic process assisted by trifluoroacetate of Pd complex via a six-membered-ring transition state. The reaction proceeds well in polar solvent TFE owing to its ability to stabilize the ionic intermediates in the Pd-H generation step. The strong Bronsted acid activator can remarkably decrease the energy barrier for both Pd-H generation and hydrogenation. The high enantioselectivity arises from a hydrogen-bonding interaction between N-H of the iminium salt and oxygen of the coordinated trifluoroacetate in the eight-membered-ring transition state for hydride transfer, while the active chiral Pd complex is a typical bifunctional catalyst, effecting both the hydrogenation and hydrogen-bonding interaction between the iminium salt and the coordinated trifluoroacetate of Pd complex. Notably, the Pd-catalyzed asymmetric hydrogenation is relatively tolerant to oxygen, acid, and water.
关键词[WOS]: HIGHLY ENANTIOSELECTIVE SYNTHESIS ;  N-HETEROCYCLIC CARBENE ;  D-2/D-4 RECEPTOR ANTAGONISTS ;  HETEROAROMATIC-COMPOUNDS ;  AEROBIC OXIDATION ;  MOLECULAR-OXYGEN ;  RHODIUM COMPLEX ;  II-HYDRIDE ;  ISOQUINOLINIUM SALTS ;  PALLADIUM(I) HYDRIDE
语种: 英语
WOS记录号: WOS:000336635400035
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/144188
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

Files in This Item: Download All
File Name/ File Size Content Type Version Access License
2014v7ccOOSBPg.PDF(3117KB)期刊论文作者接受稿开放获取View Download

作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Dalian Univ Technol, Sch Chem Engn, Inst Coal Chem Engn, State Key Lab Fine Chem, Dalian 116024, Peoples R China

Recommended Citation:
Duan, Ying,Li, Lu,Chen, Mu-Wang,et al. Homogenous Pd-Catalyzed Asymmetric Hydrogenation of Unprotected Indoles: Scope and Mechanistic Studies[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2014,136(21):7688-7700.
Service
 Recommend this item
 Sava as my favorate item
 Show this item's statistics
 Export Endnote File
Google Scholar
 Similar articles in Google Scholar
 [Duan, Ying]'s Articles
 [Li, Lu]'s Articles
 [Chen, Mu-Wang]'s Articles
CSDL cross search
 Similar articles in CSDL Cross Search
 [Duan, Ying]‘s Articles
 [Li, Lu]‘s Articles
 [Chen, Mu-Wang]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
  Add to CiteULike  Add to Connotea  Add to Del.icio.us  Add to Digg  Add to Reddit 
文件名: 2014v7ccOOSBPg.PDF
格式: Adobe PDF
此文件暂不支持浏览
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace