氨基氧化物-埃文斯乙酸混合聚合物:阿尔多尔添加与匹配和不匹配的立体控制
Janis Jermaks1, Evan H Tallmadge1, Ivan Keresztes1
1Department of Chemistry and Chemical Biology Baker Laboratory, Cornell University Ithaca, New York 14853-1301, United States.
Journal of the American Chemical Society
|February 20, 2018
概括
奇拉氨基氧化物通过形成混合四聚合物,显著增强阿尔多尔添加物的酶选择性. 这些发现为立体选择性合成提供了一个新的机制模型.
科学领域:
- 有机化学 有机化学
- 立体选择性合成 立体选择性合成
- 不对称的催化剂.
背景情况:
- 埃文斯酸盐和性化氨基氧化物是不对称合成中的关键辅助剂.
- 了解它们的立体导向能力的结构和机制基础对于开发新的合成方法至关重要.
研究的目的:
- 为了研究性氨基氧化物在增强 aldol 添加过程中的 enantioselectivity 的作用.
- 阐明埃诺酸盐和氨基氧化物之间形成的混合聚合物的结构和反应性.
主要方法:
- 混合四聚体结构的光谱测定 (2:2 和 3:1 石化测量).
- 动力学和计算研究以建模反应机制.
- 分析由反原体配对产生的匹配和不匹配的立体选择性.
主要成果:
- 发现氨基氧化物可以放大 aldol 添加物的 enantioselectivity.
- 鉴定了具有2:2和3:1 (富含氧化物) 固态度的混合四度体的结构.
- 基于3:1混合四聚体反应的机械模型被提出,尽管2:2聚合物提出了未解决的问题.
结论:
- 基拉尔氨基氧化物是阿尔多尔反应中酶选择性的有效放大剂.
- 该研究提供了对这些系统中规范立体选择性的结构基础和机制途径的见解.
- 需要进一步的研究,才能充分理解2:2混合聚合物的反应机制中的作用.
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