Asymmetric Catalysis in Radical Chemistry
Asymmetric Catalysis in Radical Chemistry
复制标题
自由基化学中的不对称催化
DOI：
10.1021/acs.chemrev.2c00622
复制
发表时间：
2022
期刊：
影响因子：
62.1
通讯作者：
Nagib, David A.
中科院分区：
文献类型：
--
作者：
Nagib, David A.
在我们的手性世界中，可以改善我们生活的分子的开发，特别是在医学和农业领域，通常需要对映选择性合成。在过去的20年里，三个诺贝尔奖已经通过（1）有机金属，（2）酶，和（3）有机催化策略认识到了解决这一挑战的新方法。这些工具最初被开发用于控制需要成对电子流动的经典有机反应机制的立体选择性。然而，最近在开发新的自由基化学方法以解决长期存在的合成挑战方面也出现了复兴。除了这些进展，人们一直在努力通过不对称催化来利用这些反应性的单电子物种。值得注意的是，控制短寿命开壳中间体的生成和立体化学拦截的挑战继续推动自由基化学和不对称催化领域的创新。本文简要概述了这些机制和里程碑以及关键的经验教训（图1）。对这些贡献的更详尽的调查也可以在西比、贝特朗和内加布以及尹和巴赫的实验室最近的评论中找到。3
In our chiral world, the development of molecules that can improve our lives especially in the areas of medicine and agriculture often requires enantioselective synthesis. In the past 20 years, three Nobel prizes have recognized novel approaches to address this challenge via (1) organometallic,(2) enzymatic, and (3) organocatalysis strategies. These tools were originally developed to control the stereoselectivity of classic organic reaction mechanisms that entail the flow of paired electrons. However, there has also been a recent renaissance in the development of new radical chemistry approaches to solve long-standing synthetic challenges. Alongside such advances, there has been a concerted effort to harness these reactive, single-electron species by asymmetric catalysis. Notably, the challenge of controlling the generation and stereochemical interception of short-lived, open-shell intermediates continues to drive innovation in both the areas of radical chemistry and asymmetric catalysis. A brief outline of these mechanisms and milestones and key takeaway lessons is included here (Figure 1). More exhaustive surveys of these contributions may also be found in recent Reviews by the laboratories of Sibi, Bertrand, and Nechab, 1 as well as by Yoon 2 and Bach. 3