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

doi:10.1021/ja071070

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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-Qiang 1; Li, Xin 1; Xia, Yuanzhi 1; Zhang, Liming 2; Yu, Zhi-Xiang 1
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2007-12-19
卷号	129 期号:50 页码:15503-15512
ISSN号	0002-7863
DOI	10.1021/ja071070
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
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000251581900034
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/62593]
专题	中国科学院化学研究所
通讯作者	Yu, Zhi-Xiang
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
推荐引用方式 GB/T 7714	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.