An Electrocatalytic Approach to the Radical Difunctionalization of Alkenes
An Electrocatalytic Approach to the Radical Difunctionalization of Alkenes
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DOI：
10.1021/acscatal.8b01069
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发表时间：
2018-06-01
期刊：
影响因子：
12.9
通讯作者：
Lin, Song
中科院分区：
文献类型：
--
作者：
Sauer, Gregory S.;Lin, Song
鉴于其许多独特的特点，电化学代表了一种有吸引力的方法，以满足有机合成的主流趋势。特别是电催化-一个集成电化学和小分子催化的过程，有可能大大提高合成电化学的范围，并提供广泛的有用的转换。最近，我们已经证明了新的催化方法，结合联合收割机电化学和氧化还原金属催化氧化双官能化的烯烃，以获得不同的阵列的邻近官能化的结构。该观点详细介绍了我们的设计原则，这些原则支持烯烃的电化学二叠氮化，二氯化和卤代三氟甲基化的发展，这些原则是建立在合成电化学，自由基化学和过渡金属催化领域其他人的基础工作上的。氧化还原活性Mn催化剂的引入允许在温和条件下在低电位下从容易获得的试剂生成自由基中间体。这些过渡金属还通过充当自由基基团转移剂而赋予对烯烃官能化过程的选择性控制。因此，我们的电催化双官能化反应表现出优异的化学选择性、广泛的底物范围和高官能团相容性。具体而言，阳极耦合电解，一种以平行方式配对两个单电子氧化事件的方法，使得能够发展烯烃的区域选择性和化学选择性异双官能化。我们在本透视图中描述的新转化的产物代表了许多医学相关化合物的相关结构。我们预计，这里提出的设计参数是通用的，并将提供一个平台，为其他具有挑战性的有机氧化还原转化的电催化系统的发展。
Given its many distinct characteristics, electrochemistry represents an attractive approach to meet the prevailing trends in organic synthesis. In particular, electrocatalysis-a process that integrates electrochemistry and small-molecule catalysis has the potential to substantially improve the scope of synthetic electrochemistry and provide a wide range of useful transformations. Recently, we have demonstrated new catalytic approaches that combine electrochemistry and redox-metal catalysis for the oxidative difunctionalization of alkenes to access a diverse array of vicinally functionalized structures. This Perspective details our design principles underpinning the development of electrochemical diazidation, dichlorination, and halotrifluoromethylation of alkenes, which were built on foundational work by others in the areas of synthetic electrochemistry, radical chemistry, and transition-metal catalysis. The introduction of redox-active Mn catalysts allows the generation of radical intermediates from readily available reagents at low potentials under mild conditions. These transition metals also impart selectivity control over the alkene functionalization processes by functioning as radical group transfer agents. As such, our electrocatalytic difunctionalization reactions exhibit excellent chemoselectivity, broad substrate scope, and high functional group compatibility. Specifically, anodically coupled electrolysis, an approach that pairs two single electron oxidation events in a parallel manner, enables the development of regio- and chemoselective heterodifunctionalization of alkenes. The products of the new transformations we describe in this Perspective represent pertinent structures in numerous medicinally relevant compounds. We anticipate that the design parameters presented here are general and will provide a platform for the development of electrocatalytic systems for other challenging organic redox transformations.