Theoretical studies on reaction pathways of Samarium(II) carbenoid-promoteded cyclopropanation reaction of ethylene

被引：4

作者：

Geng, ZY ^{[1
]}

Zhang, XH ^{[1
]}

Wang, YC ^{[1
]}

Fang, R ^{[1
]}

Gao, LG ^{[1
]}

Chen, XX ^{[1
]}

Zhao, CY ^{[1
]}

机构：

[1] NW Normal Univ, Coll Chem & Chem Engn, Gansu Province Key Lab Polymer Mat, Lanzhou 730070, Peoples R China

来源：

CHINESE JOURNAL OF CHEMICAL PHYSICS | 2006年 / 19卷 / 01期

关键词：

Samarium carbenoid; cyclopropanation; Simmons-Smith reaction; density functional theory;

D O I：

10.1360/cjcp2006.19(1).69.7

中图分类号：

O64 [物理化学（理论化学）、化学物理学]; O56 [分子物理学、原子物理学];

学科分类号：

070203 ; 070304 ; 081704 ; 1406 ;

摘要：

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 B3LY`P 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.

引用

页码：69 / 75

页数：7

共 23 条

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