Electrochemical Generation and Use in Organic Synthesis of C‐, O‐, and N‐Centered Radicals

Abstract

During the last decade several research groups have been developing electrochemical procedures to access highly functionalized organic molecules. Among the most exciting advances, the possibility of using free radical chemistry has attracted the attention of the most important synthetic groups. Nowadays, electrochemical strategies based on these species with a synthetic purpose are published continuously in scientific journals, increasing the alternatives for the synthetic organic chemistry laboratories. Free radicals can be obtained in organic electrochemical reactions; thus, this review reassembles the last decade's (2010–2020) efforts of the electrosynthetic community to generate and take advantage of the C‐, O‐, and N‐centered radicals’ reactivity. The electrochemical reactions that occur, as well as the proposed mechanism, are discussed, trying to give clear information about the used conditions and reactivity of these reactive intermediate species.

Electrocatalytic Generation of Acyl Radicals and Their Applications

“…[9] In the context of acyl radicals, electrocatalysis has also showed its unique synthetic potential to generate acyl radicals from various acyl radical precursors in sustainable manners. [10] In this review, we would like to highlight the recent advances toward the electrocatalytic generation of acyl radicals and their applications, with an emphasis on the substrate scope, reaction limitation and mechanistic concepts. The related reactions were categorized according to the pathways of acyl radical generation, including outer-sphere ET, inner-sphere ET, and HAT processes.…”

“…Recently, electrocatalysis has emerged as a mild and redox‐economical platform to obtain open‐shell intermediates [9] . In the context of acyl radicals, electrocatalysis has also showed its unique synthetic potential to generate acyl radicals from various acyl radical precursors in sustainable manners [10] . In this review, we would like to highlight the recent advances toward the electrocatalytic generation of acyl radicals and their applications, with an emphasis on the substrate scope, reaction limitation and mechanistic concepts.…”

Generation of aryl radicals fromin situactivated homolytic scission: driving radical reactions by ball milling

“…3 Electron transfer is a particularly attractive approach, as reactive radicals can be accessed from readily available starting materials by either adding an electron to the substrate or removing an electron from the substrate. Over the past few decades, redox catalysis strategies such as transition-metal catalysis, 4 photocatalysis 5 and electrocatalysis 6 have become a powerful and highly adopted tool in promoting radical reactions. Despite the advances, matching redox potentials is the key driving force for electron transfer, and thus some types of potentially useful radical intermediates remain difficult to produce.…”

Electrochemical Catalytic Hydrocarbonylation of Arylacetylenes

“…Moeller's group completed the total synthesis of the natural product arylenol A by electrochemical method, [25] while Baran's group reported the total synthesis of Teleocidins B1−B4 through the electrochemical arylamination [26] . Frontano‐Uribe's team investigated the electrochemical reduction of thiocarbonates and its application in the synthesis of a naturally occurring α‐pyrone [27] . It would be anticipated that with the further understanding and developing of the electrochemistry, such kind of environment‐friendly methods will be more and more applicable in the modern chemical syntheses [28] …”

“…[26] Frontano-Uribe's team investigated the electrochemical reduction of thiocarbonates and its application in the synthesis of a naturally occurring α-pyrone. [27] It would be anticipated that with the further understanding and developing of the electrochemistry, such kind of environment-friendly methods will be more and more applicable in the modern chemical syntheses. [28] Herein, we report an electrochemical catalytic hydrocarbonylation of the arylacetylenes under mild reaction conditions.…”