Mechanism of the Transition-Metal-Catalyzed Hydroarylation of Bromo-Alkynes Revisited: Hydrogen versus Bromine Migration
文献类型：期刊论文
| 作者 | Huang, Genping2,3; Cheng, Bing2; Xu, Liang2; Li, Yahong1; Xia, Yuanzhi2 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2012-04-01 |
| 卷号 | 18期号:17页码:5401-5415 |
| 关键词 | Alkynes Cycloisomerization Density Functional Calculations Hydroarylation Transition Metals |
| 文献子类 | Article |
| 英文摘要 | A comprehensive mechanistic study of the InCl3-, AuCl-, and PtCl2-catalyzed cycloisomerization of the 2-(haloethynyl)biphenyl derivatives of Furstner et al. was carried out by DFT/M06 calculations to uncover the catalyst-dependent selectivity of the reactions. The results revealed that the 6-endo-dig cyclization is the most favorable pathway in both InCl3- and AuCl-catalyzed reactions. When AuCl is used, the 9-bromophenanthrene product could be formed by consecutive 1,2-H/1,2-Br migrations from the Wheland-type intermediate of the 6-endo-dig cyclization. However, in the InCl3-catalyzed reactions, the chloride-assisted intermolecular H-migrations between two Wheland-type intermediates are more favorable. These Cl-assisted H-migrations would eventually lead to 10-bromophenanthrene through proto-demetalation of the aryl indium intermediate with HCl. The cause of the poor selectivity of the PtCl2 catalyst in the experiments by the Furstner group was predicted. It was found that both the PtCl2-catalyzed alkynevinylidene rearrangement and the 5-exo-dig cyclization pathways have very close activation energies. Further calculations found the former pathway would lead eventually to both 9- and 10-bromophenanthrene products, as a result of the Cl-assisted H-migrations after the cyclization of the Ptvinylidene intermediate. Alternatively, the intermediate from the 5-exo-dig cyclization would be transformed into a relatively stable Ptcarbene intermediate irreversibly, which could give rise to the 9-alkylidene fluorene product through a 1,2-H shift with a 28.1 kcal?mol-1 activation barrier. These findings shed new light on the complex product mixtures of the PtCl2-catalyzed reaction. |
| WOS关键词 | HOMOGENEOUS GOLD CATALYSIS ; C-H BOND ; EFFECTIVE CORE POTENTIALS ; GOLD(I)-CATALYZED INTRAMOLECULAR HYDROARYLATION ; CYCLOISOMERIZATION REACTIONS ; HALOGEN MIGRATION ; SKELETAL REORGANIZATION ; MOLECULAR CALCULATIONS ; ORGANIC-REACTIONS ; TERMINAL ALKYNES |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000302868100036 |
| 源URL | [http://ir.isl.ac.cn/handle/363002/5572]  |
| 专题 | 青海盐湖研究所_青海盐湖研究所知识仓储 中国科学院青海盐湖研究所 |
| 作者单位 | 1.Soochow Univ, Coll Chem Chem Engn & Mat Sci, Suzhou 215123, Peoples R China 2.Wenzhou Univ, Coll Chem & Mat Engn, Wenzhou 325035, Peoples R China 3.Chinese Acad Sci, Qinghai Inst Salt Lakes, Xining 810008, Peoples R China |
| 推荐引用方式 GB/T 7714 | Huang, Genping,Cheng, Bing,Xu, Liang,et al. Mechanism of the Transition-Metal-Catalyzed Hydroarylation of Bromo-Alkynes Revisited: Hydrogen versus Bromine Migration[J]. CHEMISTRY-A EUROPEAN JOURNAL,2012,18(17):5401-5415. |
| APA | Huang, Genping,Cheng, Bing,Xu, Liang,Li, Yahong,&Xia, Yuanzhi.(2012).Mechanism of the Transition-Metal-Catalyzed Hydroarylation of Bromo-Alkynes Revisited: Hydrogen versus Bromine Migration.CHEMISTRY-A EUROPEAN JOURNAL,18(17),5401-5415. |
| MLA | Huang, Genping,et al."Mechanism of the Transition-Metal-Catalyzed Hydroarylation of Bromo-Alkynes Revisited: Hydrogen versus Bromine Migration".CHEMISTRY-A EUROPEAN JOURNAL 18.17(2012):5401-5415. |
入库方式： OAI收割
来源：青海盐湖研究所
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