| 董琦,李海萌,尚会建.SalenMn(Ⅲ)催化的非活化烯烃分子内不对称卤胺化反应[J].分子催化,2023,37(2):164-173 |
| SalenMn(Ⅲ)催化的非活化烯烃分子内不对称卤胺化反应 |
| SalenMn(Ⅲ) Catalyze Intramolecular Asymmetric Haloalamination Reactions of Unactivated Olefin |
| 投稿时间：2022-11-24 修订日期：2023-01-28 |
| DOI：10.16084/j.issn1001-3555.2023.02.006 |
| 中文关键词: 卤胺化反应 不对称合成 SalenMn(III)配合物 氮杂环 |
| 英文关键词:aminohalogenation asymmetric synthesis salenMn(Ⅲ) nitrogen heterocycles |
| 基金项目:河北省自然科学基金(批准号: B2020208095)资助 |
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| 中文摘要: |
| 研究了一种手性SalenMn(Ⅲ)催化的非活化烯烃分子内不对称卤胺化反应, 用于不对称合成一系列手性卤代吡咯烷产物. 反应在10%(摩尔分数)的催化剂存在下, 10 ℃下反应, 以70%~90%的产率得到卤代吡咯烷产物, 对映选择性最高可达到97%. 配体合成简单, 使用量小, 反应条件温和. 猜测机理是通过氮自由基对双键的选择性加成构建手性中心. |
| 英文摘要: |
| Nitrogen heterocycle is the composition and structure of many natural products and essential substances for human body, which is widely used in the field of medicine and chemical industry. Intramolecular amination of olefins has high reactivity and is an important method to synthesize nitrogen heterocycles. The method of asymmetric catalytic reaction to obtain chiral products has the advantages of good enantioselectivity and avoiding waste. It is essential to find appropriate chiral catalysts. However, many chiral catalysts need many steps and high cost. SalenMn(Ⅲ) is an excellent chiral catalyst with simple synthesis and high yield. In this paper, a intramolecular amination of inactivated olefins which was catalyzed by SalenMn(Ⅲ)Cl was developed. The effect of solvent, temperature, catalyst and catalyst loading were investigated. React with substrates with different substituents in order to explore the scope and general applicability of the reaction. The result is than a series of chiral pyrrolidine products were obtained in 70%~90% yield, with the highest enantioselectivity of 97%. This catalyst is easy to synthesize, and use a small amount to get good results. The reaction can be carried out under mild conditions. The reaction mechanism may be through free radical addition. In this process, the product has chirality due to the steric exclusion of the ligand. |
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