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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
Shi, Fu-Qiang1; Li, Xin1; Xia, Yuanzhi1; Zhang, Liming2; Yu, Zhi-Xiang1
刊名JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2007-12-19
DOI10.1021/ja071070
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
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
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.
语种英语
WOS记录号WOS:000251581900034
引用统计
被引频次:223[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/140704
专题中国科学院大连化学物理研究所
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
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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.
APA Shi, Fu-Qiang,Li, Xin,Xia, Yuanzhi,Zhang, Liming,&Yu, Zhi-Xiang.(2007).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.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,129(50),15503-15512.
MLA Shi, Fu-Qiang,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".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 129.50(2007):15503-15512.
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