大量的性金属子使得C-N轴性性通过动态动力学分辨率实现了高效的催化不对称化
Xianghua Zhao1, Xinyu Chen1, Linxian Fan1
1State Key Laboratory of Green Chemical Synthesis and Conversion, College of Pharmaceutical Sciences, Zhejiang University of Technology Hangzhou 310014 P. R. China lingfei@zjut.edu.cn weihuizhong@zjut.edu.cn.
阳离子催化剂能够有效地不对称地化N-的基和基,从而产生轴性性. 这种方法提供了出色的立体控制和可扩展性,为新奇的性连接体开发铺平了道路.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- 阳离子诺约里型催化剂 (HM-NM) 在不对称化中提高反应速率和周转率 (TON).
- 现有的阳离子催化剂主要用于中心性,对轴性性应用有限.
研究的目的:
- 开发一种高效的阳离子催化剂,用于构建轴性性.
- 通过动态动力学分辨率探索N-的非对称化N-英多尔基和化物.
主要方法:
- 设计和合成一种新型三联体框架 (Huaphos).
- 开发一种使用华配体的阳离子催化剂 (HIr-NCs).
- 在温和条件下在不对称化中应用催化剂.
- 密度功能理论 (DFT) 研究以阐明反应机制.
主要成果:
- 阳离子催化剂 (HIr-NCs) 在N-基和基的不对称化中实现了优异的立体控制 (高达99% ee和99:1 dr).
- DFT研究表明,离子和基质之间的静电相互作用显著降低了激活屏障,加速了反应速率.
- 该协议证明了可扩展到克数量的可扩展性,具有非常低的催化剂负载 (S/C = 40,000).
结论:
- 开发的阳离子铁催化剂通过不对称化有效地构建了轴性性.
- 该协议提供了一种温和,高效和可扩展的方法来合成有价值的性化合物.
- 由此产生的化产品可以成为用于不对称催化剂的新型性配体的前体.
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