Organic Synthesis base on computational results : in-plane S_N2 reaction of haloalkenes

基于计算结果的有机合成：卤代烯烃的面内S_N2反应

• 批准号: 15590014
• 负责人: ANDO Kaori
• 金额: $ 1.6万
• 依托单位: University of the Ryukyus
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15590014/
• 关键词: S_N2 reaction on the sp^2 carbon; addition-elimination; transition state; density functional calculation; intramolecular reaction; SP^2炭素でのS_N2反応; sp^2炭素でのS_N2反応; 溶媒効果; 活性化エネルギー; ハロアルケンへの分子内求核置換反応

The intramolecular nucleophilic cylization of haloalkenes was studied at the B3LYP/6-31+G(d) level in an Onsager continuum model for DMF(_=37.06). The reaction of (E)-2-(2-chloro-1-methylvinyl)phenol(E-1) takes a concerted in-plain σ-type S_N2 pathway with inversion at the sp^2 carbon with the activation free energy of 14.4 kcal/mol in DMF (17.1 kcal/mol in the gas phase). On the other hand, only π-addition transition structures were obtained from both Z-1 and the corresponding dichloroalkene with much higher activation free energies. These predictions were confirmed experimentally. We prepared haloalkenes 1. The E- and Z-isomers were separated by column chromatography and the geometries of the olef parts were determined by NOE experiments. When E-1 and Z-1 were treated with NaH in DMF, benzofuran was obtained in 95% yield from E-1, while Z-1 was recovered quantitatively even after heating at 110℃.

在B3 LYP/6-31+G（d）水平上，采用Onsager连续介质模型研究了卤代烯烃在DMF（_=37.06）中的分子内亲核环化反应.（E）-2-（2-氯-1-甲基乙烯基）苯酚（E-1）在DMF（气相）中的反应为σ-型S_N_2反应，活化自由能为14.4 kcal/mol（气相为17.1 kcal/mol）。另一方面，Z-1和相应的二氯烯烃只得到π-加成过渡结构，具有高得多的活化自由能。这些预测得到了实验的证实。我们制备了卤代烯烃1。通过柱色谱法分离E-和Z-异构体，并通过NOE实验确定烯烃部分的几何构型。当E-1和Z-1在DMF中用NaH处理时，E-1以95%的产率得到苯并呋喃，而Z-1即使在110℃加热后也能定量回收。

项目成果

A theoretical study on the origin of π-facial stereoselectivity in the alkylation of enolates derived from 4-substituted γ-butyrolactones

• DOI: 10.1021/ja044995n
• 发表时间: 2005-03-23
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Ando, K

Theoretical and experimental study on the in-plane S_N2-type substitution reaction of haloalbones with inversion of configuration at the Sp^2 carbon

卤代烃面内S_N2型Sp^2碳构型反转取代反应的理论与实验研究

• 发表时间: 2004
• 期刊: Organic Letters 6
• 作者: Tokuda;R. et al.;Hitoshi Abe;Kaori Ando
• 通讯作者: Kaori Ando

A theoretical study on the origin of π-facial stereoselectivity in the alkylation of enolates derived from 4-substututed γ-butyrolactones

4-取代γ-丁内酯烯醇化物烷基化π面立体选择性起源的理论研究

• 发表时间: 2005
• 期刊: J.Am.Chem.Soc. 127
• 作者: Kaori Ando

Organic synthesis based on computational Results

基于计算结果的有机合成

• 发表时间: 2004
• 期刊: Chemistry & Chemical Industry 57
• 作者: Kaori Ando;Kaori Ando
• 通讯作者: Kaori Ando

A Theoretical study on the origin of π-facial stereoselectivity in the alkylation of enolates derived from 4-sufstituted γ-butyrolactones

4-取代γ-丁内酯烯醇化物烷基化中π面立体选择性起源的理论研究

• 期刊: J.Am.Chem.Soc. (in the press)
• 作者: 森江泰子;他;Kaori Ando
• 通讯作者: Kaori Ando