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题名: DFT study of the mechanisms of in water Au(I)-catalyzed tandem [3,3]-rearrangement/Nazarov reaction/[1,2]-hydrogen shift of enynyl acetates: A proton-transport catalysis strategy in the water-catalyzed [1,2]-hydrogen shift
作者: Shi, Fu-Qiang1;  Li, Xin1;  Xia, Yuanzhi1;  Zhang, Liming2;  Yu, Zhi-Xiang1
刊名: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
发表日期: 2007-12-19
DOI: 10.1021/ja071070
卷: 129, 期:50, 页:15503-15512
收录类别: SCI
文章类型: Review
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Multidisciplinary
研究领域[WOS]: Chemistry
英文摘要: A computational study with the Becke3LYP density functional was carried out to elucidate the mechanisms of Au(I)-catalyzed reactions of enynyl acetates involving tandem [3,3] -rearrangement, Nazarov reaction, and [1,2]-hydrogen shift. Calculations indicate that the [3,3]-rearrangement is a two-step process with activation free energies below 10 kcal/mol for both steps. The following Nazarov-type 4 pi electrocyclic ring-closure reaction of a Au-containing dienyl cation is also easy with an activation free energy of 3.2 kcal/mol in CH2Cl2. The final step in the catalytic cycle is a [1,2]-hydride shift, and this step is the rate-limiting step (with a computed activation free energy of 20.2 kcal/mol) when dry CH2Cl2 is used as the solvent. When this tandem reaction was conducted in wet CH2Cl2, the [1,2]-hydride shift step in dry solution turned to a very efficient water-catalyzed [1,2]-hydrogen shift mechanism with an activation free energy of 16.4 kcal/mol. Because of this, the tandem reaction of enynyl acetates was found to be faster in wet CH2Cl2 as compared to the reaction in dry CH2Cl2. Calculations show that a water-catalyzed [1,2]-hydrogen shift adopts a proton-transport catalysis strategy, in which the acetoxy group in the substrate is critical because it acts as either a proton acceptor when one water molecule is involved in catalysis or a proton-relay stabilizer when a water cluster is involved in catalysis. Water is found to act as a proton shuttle in the proton-transport catalysis strategy. Theoretical discovery of the role of the acetoxy group in the water-catalyzed [1,2]-hydrogen shift process suggests that a transition metal-catalyzed reaction involving a similar hydrogen shift step can be accelerated in water or on water with only a marginal effect, unless a proton-accepting group such as an acetoxy group, which can form a hydrogen bond network with water, is present around this reaction's active site.
关键词[WOS]: DIELS-ALDER REACTIONS ;  DENSITY-FUNCTIONAL THEORY ;  POLARIZABLE CONTINUUM MODEL ;  ORGANIC-REACTIONS ;  GAS-PHASE ;  RADICAL CATIONS ;  ALDOL REACTION ;  FREE-ENERGIES ;  NAZAROV CYCLIZATION ;  GOLD CATALYSIS
语种: 英语
WOS记录号: WOS:000251581900034
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/140704
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.Peking Univ, Coll Chem, Key Lab Bioorgan Chem & Mol Engn, Beijing Natl Lab Mol Sci,Minist Educ, Beijing 100871, Peoples R China
2.Univ Nevada, Dept Chem, Reno, NV 89557 USA

Recommended Citation:
Shi, Fu-Qiang,Li, Xin,Xia, Yuanzhi,et al. DFT study of the mechanisms of in water Au(I)-catalyzed tandem [3,3]-rearrangement/Nazarov reaction/[1,2]-hydrogen shift of enynyl acetates: A proton-transport catalysis strategy in the water-catalyzed [1,2]-hydrogen shift[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2007,129(50):15503-15512.
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