A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

Abstract

The direct exploitation of ‘electrons’ as reagents in synthetic organic transformations is on the verge of a renaissance by virtue of its greenness, sustainability, atom economy, step economy and inherent safety. Achieving stereocontrol in such organic electrochemical reactions remains a major synthetic challenge and hence demands great expertise. This review provides a comprehensive discussion of the details of stereoselective organic electrochemical reactions along with the synthetic accomplishments achieved with these methods.

Making electrochemistry easily accessible to the synthetic chemist

“…The advantages of the setup employed will be discussed for each type of reaction. See the following reviews for specific transformations: cross coupling, [24][25][26] CH activation, [27][28][29][30][31][32][33][34][35][36] asymmetric synthesis, 14 heterocycle formation, [37][38][39] arylation, 40 fluorination, 41 organometallic catalysis, 42,43 cation pool method. 44 The different types of reactions can be summarised as: (1) direct electrochemical reaction with solvent degradation as counter reaction, (2) direct electrochemical reaction with nonsolvent degradation as counter reaction, (3) mediated or catalysed electrochemical reaction, (4) redox combined electrochemical reaction (Fig.…”

“…During the last decade, electrochemistry has received renewed interest as a tool for synthetic chemistry. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] This is exemplified by whole journal issues being dedicated to synthetic electrochemistry. 18,19 Electrochemistry offers a very mild and atom efficient method to achieve selective oxidative or reduc-tive transformations using electrons as reactants.…”

“…This tutorial review provides an introduction to electrochemistry and is not designed to be an extensive review of all synthetic electrochemical examples. For further information recent reviews and the references therein are recommended: certain transformations including cross coupling, [24][25][26] CH activation, [27][28][29][30][31][32][33][34][35][36] asymmetric synthesis, 14 heterocycle formation, [37][38][39] arylation, 40 fluorination, 41 organometallic catalysis, 42,43 cation pool method, 44 continuous reactor types, [45][46][47][48][49][50][51][52][53][54][55] analytical tools 56,57 and general reviews and perspectives. [1][2][3][4][5][6][7][8][9][10][11][12][13]…”

The preparation and applications of amides using electrosynthesis

“…54 A similar approach has been reported by Lee for the diastereoselective cyclisation of hydroxylamides. 55,56 Finally, the use of Shono-type oxidation has even been extended to the selective deethylation of tertiary amides (a common pharmaceutical moiety) in a metabolism-mimicking protocol, as reported by Bal and co-workers in 2019. 57 The N-dealkylation of drug molecules is a common metabolism pathway facilitated by cytochrome P450.…”

Merging Electrosynthesis and Bifunctional Squaramide Catalysis in the Asymmetric Detrifluoroacetylative Alkylation Reactions

“…[1,2] Specially, the advances in asymmetric catalytic electrochemistry has emerged as a powerful strategy for the sustainable generation of reactive intermediates in the construction of enantioenriched molecular scaffolds. [3,4] A central theme of catalytic enantioselective electrosynthesis from a common precursor in a rational and predictable manner, especially embedded in the synthetically interesting, is the identification of reliable strategies to forge new carbon-carbon bonds with high levels of stereoselectivity. [5] Moreover, reactions involving electrochemical process pose a further difficult due to the stability and compatibility between the asymmetric catalytic system and electrochemical system.…”