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Theoretical Studies on Reaction Pathways of Samarium(Ⅱ) Carbenoid-Promoteded Cyclopropanation Reaction of Ethylene
Zhi-yuan Geng*,Xing-hui Zhang,Yong-cheng Wang,Ran Fang,Li-guo Gao,Xiao-xia Chen,Cun-yuan Zhao
Author NameAffiliation
Zhi-yuan Geng* College of Chemistry and Chemical Engineering,Gansu Province Key Laboratory of Polymer Materials Northwest Normal University,Lanzhou 730070,China 
Xing-hui Zhang College of Chemistry and Chemical Engineering,Gansu Province Key Laboratory of Polymer Materials Northwest Normal University,Lanzhou 730070,China 
Yong-cheng Wang College of Chemistry and Chemical Engineering,Gansu Province Key Laboratory of Polymer Materials Northwest Normal University,Lanzhou 730070,China 
Ran Fang College of Chemistry and Chemical Engineering,Gansu Province Key Laboratory of Polymer Materials Northwest Normal University,Lanzhou 730070,China 
Li-guo Gao College of Chemistry and Chemical Engineering,Gansu Province Key Laboratory of Polymer Materials Northwest Normal University,Lanzhou 730070,China 
Xiao-xia Chen College of Chemistry and Chemical Engineering,Gansu Province Key Laboratory of Polymer Materials Northwest Normal University,Lanzhou 730070,China 
Cun-yuan Zhao College of Chemistry and Chemical Engineering,Gansu Province Key Laboratory of Polymer Materials Northwest Normal University,Lanzhou 730070,China 
Abstract:
In order to have efficient and highly stereoselective cyclopropanating reagents, the cyclopropanation reaction of ethylene promoted with Samarium(Ⅱ) carbenoid [Simmons-Smith(SS)reagent] were studied by means of B3LYP hybrid density functional method. The geometries for reactants, transition states and products are completely optimized. All transition states were verified by the vibrational analysis and the intrinsic reaction coordinate (IRC) calculations. The results showed that, identical with the lithium carbenoid,CH3SmCH2X(X=Cl, Br and I) can fairly react with ethylene via both methylene transfer pathway (pathway A) and carbometalation pathway (pathway B). And the cyclopropanation reaction via methylene transfer pathway proceeds with a lower barrier and at lower temperatures.
Key words:  Samarium carbenoid, Cyclopropanation, Simmons-Smith reaction, Density functional theory
FundProject:
钐(Ⅱ)类卡宾CH3SmCH2X(X=Cl、Br和I)促进乙烯环丙烷化反应途径的理论研究
耿志远*,张兴辉,王永成,方冉,高立国,陈晓霞,赵存元
摘要:
用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理.对三种不同的钐的SS试剂CH3SmCH2X(其中X=Cl、Br和I)分别和CH2CH2反应的各反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证.结果表明:CH3SmCH2X(其中X=Cl、Br和I)与CH2CH2环丙烷化反应按亚甲基转移通道(通道A)和卡宾金属化通道(通道B)都可以进行,与锂类卡宾的反应机理相同,只是按亚甲基转移通道(通道A)进行反应较容易一些,而且此反应在较低的温度下就可以发生.
关键词:  钐类卡宾  环丙烷化  Simmons-Smith反应  密度泛函
DOI:10.1360/cjcp2006.19(1).69.7
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