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题名: Reaction Mechanism and Chemoselectivity of Intermolecular Cycloaddition Reactions between Phenyl-Substituted Cyclopropenone Ketal and Methyl Vinyl Ketone
作者: Qiao, Yan1;  Chu, Tian-Shu1, 2
刊名: JOURNAL OF ORGANIC CHEMISTRY
发表日期: 2011-05-06
DOI: 10.1021/jo102454y
卷: 76, 期:9, 页:3086-3095
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Organic
研究领域[WOS]: Chemistry
英文摘要: In this paper, the mechanisms of the intermolecular [3 + 2] and [1 + 2] cycloaddition reactions of 1,1/1,3-dipolar pi-delocalized singlet vinylcarbenes, which is. obtained from cyclopropenone, with an electron-deficient C=O or C=C dipolarophile, to generate five-membered ring products are first disclosed by the density functional theory (DFT). Four reaction pathways, including two concerted [3 + 2] cycloaddition reaction pathways and two stepwise reaction pathways (an initial [1 + 2] cycloaddition and then a rearrangement from the [1 + 2] cycloadducts to the final [3 + 2] cycloadducts), are investigated at the B3LYP/6-31G(d,p) level of theory. The calculated results reveal that, in contrast to the concerted C=O [3 + 2] cycloaddition reaction pathway, which is 7.1 kcal/mol more energetically preferred compared with its stepwise reaction pathway, the C=C dipolarophile favors undergoing [1 + 2] cycloaddition rather than concerted [3 + 2] cycloaddition (difference of 5.3 kcal/mol). The lowest free energy barrier of the C=O concerted [3 + 2] cycloaddition reaction pathway shows that it predominates all other reaction pathways. This observation is consistent with the finding that the C=O [3 + 2] cycloadduct is the main product under experimental conditions. In addition, natural bond orbital second-order perturbation charge analyses are carried out to explain the preferred chemoselectivity of C=O to the C=C dipolarophile and the origins of cis-stereoselectivity for C=C [1 + 2] cycloaddition. Solvent effects are further considered at the B3LYP/6-31G(d,p) level in the solvents CH(3)CN, DMF, THF, CH(2)Cl(2), toluene, and benzene using the PCM model. The results indicate that the relative reaction trends and the main products are insensitive to the polarity of the reaction solvent.
关键词[WOS]: DELOCALIZED SINGLET VINYLCARBENES ;  ASYMMETRIC 3+2 CYCLOADDITION ;  ELECTRON-DEFICIENT OLEFINS ;  DENSITY-FUNCTIONAL METHODS ;  CONTAINING CARBONYL YLIDES ;  VIBRATIONAL FREQUENCIES ;  BASIS-SETS ;  ENANTIOSELECTIVE CONSTRUCTION ;  1,3-DIPOLAR CYCLOADDITION ;  2-CARBON CYCLOADDITION
语种: 英语
WOS记录号: WOS:000289956900013
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142474
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.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Qingdao Univ, Inst Computat Sci & Engn, Lab New Fiber Mat & Modern Text, Growing Base State Key Lab, Qingdao 266071, Peoples R China

Recommended Citation:
Qiao, Yan,Chu, Tian-Shu. Reaction Mechanism and Chemoselectivity of Intermolecular Cycloaddition Reactions between Phenyl-Substituted Cyclopropenone Ketal and Methyl Vinyl Ketone[J]. JOURNAL OF ORGANIC CHEMISTRY,2011,76(9):3086-3095.
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