在Enantioselective继电反应中中断链路的发展和机械质疑
Sean P Ross1, Ajara A Rahman1, Matthew S Sigman1
1Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States.
Journal of the American Chemical Society
|May 16, 2020
概括
研究人员开发了一种方法,通过改变氨基保护组来控制-复合物的链路行走. 这允许选择性功能化,产生胺或胺,提供新的合成策略.
科学领域:
- 有机化学
- 催化剂
- 反应机制
背景情况:
- 的核化形成中间体,使各种反应成为可能.
- -中间体可以经历"链路行走",允许远程功能化.
- 选择性地在特定地点中断链路行走仍然是一个挑战.
研究的目的:
- 开发选择性中断链行走的方法.
- 研究氨基保护群对反应选择性的影响.
- 为了阐明链路行走和终结的机制,在enantioselective继电器赫克反应.
主要方法:
- 使用同质保护氨基的酶选择性继电器赫克反应.
- 为了控制选择性,对氨基保护组进行系统的变化.
- 计算研究 (DFT) 和同位素标记实验以探测反应机制.
主要成果:
- 通过改变氨基保护组来证明精选合成胺或胺.
- 确定了热力学控制作为选择性的驱动力,由中间稳定性控制.
- 提供了链路走路和终止步骤的机制见解.
结论:
- -复合物的链路行走可以通过操纵热力学因素来精确控制.
- 改变氨基保护组为指导反应途径提供了一种可行的策略.
- 这项工作为开发基于受控链路的新合成方法提供了基础.
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