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题名: Density Functional Theory Study of the Mechanisms and Stereochemistry of the Rh(I)-Catalyzed Intramolecular [3+2] Cycloadditions of 1-Ene- and 1-Yne-Vinylcyclopropanes
作者: Jiao, Lei1;  Lin, Mu1;  Yu, Zhi-Xiang1
刊名: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
发表日期: 2011-01-26
DOI: 10.1021/ja107396t
卷: 133, 期:3, 页:447-461
收录类别: SCI
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: The mechanisms, structures of all stationary points involved, and kinetic and thermodynamic parameters of the Rh(I)-catalyzed intramolecular [3+2] cycloaddition reactions of 1-ene- and 1-yne-vinylcyclopropanes (1-ene-VCPs and 1-yne-VCP5) have been investigated using density functional theory (DFT) calculations. The computational results showed that the [3+2] reactions of 1-ene/yne-VCPs studied here occur through a catalytic cycle of substrate catalyst complex formation, cyclopropane cleavage, alkene/alkyne insertion, and reductive elimination. Alkene/alkyne insertion is the rate-and stereoselectivity-determining step of these multistep [3+2] cycloadditions. The experimentally observed high reactivity of 1-yne-VCPs compared to 1-ene-VCPs is well rationalized by the differences of steric effects in the alkyne/alkene insertion transition states. DFT calculations unveiled that the relative orientation of the tethers in the 1-ene/yne-VCPs plays a key role in controlling the stereochemistry of the [3+2] cycloadducts. In addition, DFT calculation results are used to explain why, in some cases, the formation of the beta-hydride elimination byproduct can compete with the [3+2] pathway.
关键词[WOS]: CATALYZED 5+2 CYCLOADDITIONS ;  DIELS-ALDER REACTION ;  ASYMMETRIC TOTAL-SYNTHESIS ;  (-)-PSEUDOLARIC ACID-B ;  PAUSON-KHAND REACTION ;  ENE-VINYLCYCLOPROPANES ;  ALKENYL CYCLOPROPANES ;  ALKYNES ;  STEREOSELECTIVITY ;  ALLENES
语种: 英语
WOS记录号: WOS:000287553000016
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142466
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, Beijing Natl Lab Mol Sci, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China

Recommended Citation:
Jiao, Lei,Lin, Mu,Yu, Zhi-Xiang. Density Functional Theory Study of the Mechanisms and Stereochemistry of the Rh(I)-Catalyzed Intramolecular [3+2] Cycloadditions of 1-Ene- and 1-Yne-Vinylcyclopropanes[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2011,133(3):447-461.
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