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题名: Theoretical investigations toward the tandem reactions of N-aziridinyl imine compounds forming triquinanes via trimethylenemethane diyls: mechanisms and stereoselectivity
作者: Qiao, Yan1;  Han, Ke-Li1
刊名: ORGANIC & BIOMOLECULAR CHEMISTRY
发表日期: 2014
DOI: 10.1039/c3ob42115e
卷: 12, 期:8, 页:1220-1231
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, we have investigated the tandem reaction mechanism for the N-aziridinyl imine compounds forming triquinanes via trimethylenemethane (TMM) diyls in detail. Based on the calculated results, the reaction is initiated by the cleavage of the N-aziridinyl in the substrate, followed by an intramolecular 1,3-dipolar (3 + 2) cycloaddition preferentially leading to a linearly-fused tetrahydrocyclopentapyrazole intermediate. Next, the intermediate loses N-2 to form the singlet TMM diyl M3S, which can then undergo another concerted (3 + 2) cycloaddition to generate the linearly-fused cis-trans or cis-syn triquinane products. In addition, M3S can also undergo intersystem crossing to the triplet TMM diyl M3T, and the six possible reaction pathways associated with M3T have also been identified. The calculated results reveal that the cis-trans fused pathway associated with M3S is energetically preferred with the highest free energy barrier of 25.0 kcal mol(-1). In comparison, the cyclization of M3T requires much higher activation free energies (Delta G(not equal) = 34.4-57.8 kcal mol(-1)). At the experimental temperature 110 degrees C, only the linearly-fused cis-trans and cis-syn pathways associated with M3T (Delta G(not equal) = 34.4 and 35.5 kcal mol(-1) respectively) are possible. The calculated results also indicate that for both M3S and M3T, the linearly-fused cis-trans triquinane should be the main product, which is consistent with the experimental observation. At last, conformational and NBO analyses on key transition states identified the cis-trans stereocontrol factors. Further calculations indicate that the methyl substituent on the allene group of the reactant substrate improves the stereoselectivity of the reaction but does not affect the rate-determining step.
关键词[WOS]: POLARIZABLE CONTINUUM MODEL ;  DIELS-ALDER REACTIONS ;  1,3-DIPOLAR CYCLOADDITION ;  COMPUTATIONAL EVIDENCE ;  GEOMETRY OPTIMIZATION ;  CYCLIZATION CASCADE ;  ELECTRONIC STATES ;  ALLENYL AZIDES ;  EXCITED-STATES ;  GROUND-STATE
语种: 英语
WOS记录号: WOS:000330792500007
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/143202
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

Recommended Citation:
Qiao, Yan,Han, Ke-Li. Theoretical investigations toward the tandem reactions of N-aziridinyl imine compounds forming triquinanes via trimethylenemethane diyls: mechanisms and stereoselectivity[J]. ORGANIC & BIOMOLECULAR CHEMISTRY,2014,12(8):1220-1231.
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