用循环 Racemic 起始材料对 Cu 催化不对称的基化进行机制研究
Emeline Rideau1, Hengzhi You1, Mireia Sidera1
1Department of Chemistry, Chemistry Research Laboratory, University of Oxford , 12 Mansfield Road, Oxford, OX1 3TA, U.K.
Journal of the American Chemical Society
|April 1, 2017
概括
铜催化剂通过形成复杂的寡合物种来促进对化物不对称的添加. 这些催化剂将起始物质拉塞化,并选择性地产生一个动态动态不对称的变化.
科学领域:
- 有机金属化学
- 不对称的催化
背景情况:
- 铜催化不对称反应对于合成性分子至关重要.
- 了解这些反应的机制,特别是动态动态不对称转换,是开发新催化系统的关键.
研究的目的:
- 阐明Cu-催化不对称添加到赛米电友的机制.
- 研究寡合铜联体复合体和对子体在催化中的作用.
- 开发新的反应条件和配体,以提高酶选择性和基质范围.
主要方法:
- 涉及同位素标记,NMR光谱 (动力和动态) 和动力建模的机制研究.
- 结构-活性关系分析和开发新的胺配体.
- 对酸和酸中间体的研究.
主要成果:
- 在反应过程中,Oligomeric Cu-ligand 复合物进化,增强了反应速度和酶选择性.
- 通过酸中间体,Cu- counterions 影响路径选择和种族化.
- 新的D连接体使得对racemic酸盐和七个环酸具有高度选择性的添加.
结论:
- 拟议的机制涉及复杂的寡合酶催化剂,它们既能对基质进行种族化,又能达到高的反选择性.
- 这项工作提供了更广泛的动态动态不对称转换的见解.
- 这些发现有望促进铜催化不对称反应的扩展.
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