Theoretical Study of the AlEt3-Promoted Tandem Reductive Rearrangement of Epoxides |
| |
Authors: | Li-dong Zhang Hui-jun Guo Yang Pan Fei Qi |
| |
Institution: | {{each article.affiliations aff i}}
{{if aff.addressEn && aff.addressEn != ""}}
{{if aff.label && aff.label != "" && article.affiliations.length != 1}}{{@ aff.label}}.{{/if}}{{@ aff.addressEn}}{{/if}}
{{/each}} |
| |
Abstract: | The AlEt3-promoted tandem reductive rearrangement reactions of epoxides was studied at B3LYP/6-31G(d,p) level. For the model compound σ-hydroxy epoxides, two possible reaction pathways I and II were calculated. The main difference is the order of ethylene release and six- to five-member ring rearrangement.The ring contraction rearrangement in pathway I is the first step and this step is the rate controlling step with a free energy barrier of 116.62 kJ/mol. For pathway II, the ethylene release occurs first, and is followed by a six-member ring opening reaction which is the rate controlling step, and the barrier is 251.38 kJ/mol.The reason for such high barrier is that the ethylene release results in the following reaction being moredifficult. The results show that pathway I (C-C rearrangement and then ethylene release) is more favorable,which is consistent with experimental results. |
| |
Keywords: | AlEt3 Rearrangement Density functional theory Diol Epoxide |
|
| 点击此处可从《化学物理学报(中文版)》浏览原始摘要信息 |
| 点击此处可从《化学物理学报(中文版)》下载免费的PDF全文 |