Electrochemical Methods as Enabling Tools for Glycosylation

Abstract

Electrochemical methods have been widelyu sed for organic synthesis including glycosylation. Electrochemical oxidation via single electron transfer (SET) is ap owerful method to activate varioust ypes of glycosyl donors. Their oxidation potentials, which reflect the reactivity of glycosyl donors under anodic oxidation conditions are tunable by changing protecting groups and the anomeric leaving groups of glycosyl donors. Not only thioglycosides but also other chalcogenoglycosides have been studied as highly reactive glycosyld onors.R ecently,a utomated electrochemical assembly,w hich is an automated electrochemical solutionphase synthesis of oligosaccharides was successfully demonstrated by the rational optimization of thioglycosides as both glycosyl donors and acceptors through electrochemical measurements and DFT calculations.[a] S. Manmode, Prof. T. Nokami, Prof. T. Itoh

Electrocatalytic Oxidative Transformation of Organic Acids for Carbon–Heteroatom and Sulfur–Heteroatom Bond Formation

“…The triflate group can be displaced by an alcohol to construct a β‐selective glycosyl linkage. Because this field has been discussed by other reviews, we do not reiterate it in depth here.…”

Transition-metal-free C–S bond cleavage and transformation of organosulfur compounds

“…3 Moreover, organic photochemical and electrochemical strategies have also provided remarkable approaches to the C–S bond cleavage of organosulfur compounds under transition-metal-free conditions. 4,5…”

Electrochemical Bromination of Glycals

“…Organic electrosynthesis is of current interest as one of the most promising methods for the efficient, sustainable, and green synthesis of medicinally significant compounds ( Francke and Little, 2014 ; Horn et al, 2016 ; Liang and Zeng, 2020 ; Meyer et al, 2020 ; Yuan et al, 2021 ). In recent years, the electrochemical synthesis of oligosaccharides has been successfully demonstrated through the activation of different types of glycosyl donors, such as thio-, seleno-, and telluro-glycosides ( Nokami et al, 2015 ; Manmode et al, 2018 ; Zhang et al, 2020 ). In addition, our group has been involved in the electrochemical transformation of glycals to obtain significant synthetic carbohydrate compounds ( Liu et al, 2020 ; Liu et al, 2021 ).…”