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Reaction Mechanism and Chemoselectivity of Intermolecular Cycloaddition Reactions between Phenyl-Substituted Cyclopropenone Ketal and Methyl Vinyl Ketone
Qiao, Yan1; Chu, Tian-Shu1,2
刊名JOURNAL OF ORGANIC CHEMISTRY
2011-05-06
DOI10.1021/jo102454y
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
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
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.
语种英语
WOS记录号WOS:000289956900013
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文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/142474
专题中国科学院大连化学物理研究所
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
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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.
APA Qiao, Yan,&Chu, Tian-Shu.(2011).Reaction Mechanism and Chemoselectivity of Intermolecular Cycloaddition Reactions between Phenyl-Substituted Cyclopropenone Ketal and Methyl Vinyl Ketone.JOURNAL OF ORGANIC CHEMISTRY,76(9),3086-3095.
MLA Qiao, Yan,et al."Reaction Mechanism and Chemoselectivity of Intermolecular Cycloaddition Reactions between Phenyl-Substituted Cyclopropenone Ketal and Methyl Vinyl Ketone".JOURNAL OF ORGANIC CHEMISTRY 76.9(2011):3086-3095.
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