| Isomers and [2,3]-Sila-wittig Rearrangement of [（Allyloxy）silyl]lithium Silylenoid in the Gas Phase and THF Solvent |
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| 引用本文： | XIE Ju,;FENG Da-Cheng,;YIN Ya-Xing. Isomers and [2,3]-Sila-wittig Rearrangement of [（Allyloxy）silyl]lithium Silylenoid in the Gas Phase and THF Solvent[J]. 结构化学, 2008, 0(7): 858-864 |
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| 作者姓名： | XIE Ju, FENG Da-Cheng, YIN Ya-Xing |
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| 作者单位： | College of Chemistry and Chemical Engineering Yangzhou University，School of Chemistry and Chemical Engineering Shandong University，College of Chemistry and Chemical Engineering Yangzhou University，Yangzhou 225002 China，Jinan 250100 China，Yangzhou 225002 China |
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| 基金项目： | Supported by PhD Special Research Foundation of Chinese Education Department （No. 20040422010）, and the Scientific Research Foundation of Yangzhou University |
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| 摘 要： | Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid （C3H5O）H2SiLi, 1-7, are found. The [2,3]-silawittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the aUyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of SiC（3） bond and the break of O-C（1） bond. Finally, the （allylsilyl）oxylithium （C3H5）H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate （IRC） calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work.
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| 关 键 词： | 异构体 重整 烯丙氧基甲基氧烷锂 气相 Sila-wittig反应 |
Isomers and [2,3]-Sila-wittig Rearrangement of [(Allyloxy)silyl]lithium Silylenoid in the Gas Phase and THF Solvent |
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| XIE Jua FENG Da-Chengb YIN Ya-Xinga a. Isomers and [2,3]-Sila-wittig Rearrangement of [(Allyloxy)silyl]lithium Silylenoid in the Gas Phase and THF Solvent[J]. Chinese Journal of Structural Chemistry, 2008, 0(7): 858-864 |
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| Authors: | XIE Jua FENG Da-Chengb YIN Ya-Xinga a |
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| Abstract: | Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [(allyl-oxy)silyl]lithium (C3H5O)H2SiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid (C3H5O)H2SiLi, 1~7, are found. The [2,3]-sila-wittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the allyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of Si– C(3) bond and the break of O–C(1) bond. Finally, the (allylsilyl)oxylithium (C3H5)H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate (IRC) calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work. |
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| Keywords: | silylenoid (C3H5O)H2SiLi isomer rearrangement G3MP2B3 |
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