C‐Glycosides, Array‐based Addressable Libraries, and the Versatility of Constant Current Electrochemistry

Abstract

Constant current electrochemical reactions are very versatile tools for conducting oxidation and reduction reactions. In the reactions, the potential at the working electrode automatically adjusts to that of the substrate in solution, a situation that allows for the same overall synthetic approach to be used for both the direct oxidation and reduction of substrates and the generation of a wide range of chemical reagents and catalysts. The science presented in this manuscript illustrates how a combination of these methods can be used to create new opportunities for synthesis. Specifically, a direct constant current electrolysis was used to synthesize C‐glycoside derivatives that were then placed site‐selectively on a microelectrode array by using the same overall electrochemical approach to generate chemical reagents.

Anodic Cyclizations, Densely Functionalized Synthetic Building Blocks, and the Importance of Recent Mechanistic Observations

“…Since it initially appeared that the cyclization reactions proceeded in higher yields with the use of a vinylsulfide-derived radical cation (Scheme ), efforts to deprotect the aldehyde side chain in the presence of the acid-sensitive acetonide protecting group began with a focus on the mixed acetal product 4a (Scheme ). The plan called for conversion of the mixed O,S-acetal to a dimethoxy acetal using a method that we did earlier, and then cleavage of the dimethoxy acetal in the presence of an acetonide . However, the use of that approach was bothersome because in our hands, the method for converting the mixed O,S-acetal to the dimethoxy acetal required the use of stoichiometric mercury.…”

“…The plan called for conversion of the mixed O,S-acetal to a dimethoxy acetal using a method that we did earlier, and then cleavage of the dimethoxy acetal in the presence of an acetonide. 16 the use of that approach was bothersome because in our hands, the method for converting the mixed O,S-acetal to the dimethoxy acetal required the use of stoichiometric mercury.…”

Electrochemical strategies for C–H functionalization and C–N bond formation

“…Here, atom-economical and regioselective platforms for direct functionalization of double or triple bonds allow access to a range of functionalized products, thereby offering considerable opportunities for strategic chemical synthesis. In addition to the intramolecular anodic olefin coupling reactions discussed in the previous section, other carbon- [849][850][851][852][853][854][855][856][857][858][859][860][861][862] as well as oxygen-based [863][864][865][866][867][868][869][870][871][872][873][874][875] nucleophiles have also been utilized in radical cation-initiated cyclization protocols for constructing C-C and C-O bonds, respectively. Furthermore, Moeller and coworkers have designed systems for direct functionalization of alkenes using nitrogen functionalities as trapping groups.…”

Capitalizing on Mediated Electrolyses for the Construction of Complex, Addressable Molecular Surfaces

“…The anodic oxidation approach offered a way to avoid this complexity. The method utilized was a constant current electrolysis where the potential at the anode was allowed to simply adjust to whatever substrate was present. , In each case, the potential at the anode climbed until it reached that of the substrate to be oxidized and then held constant at that point until the majority of the substrate was consumed (at which case the potential would start to climb again). The result was a selective oxidation of all three substrates using the exact same method.…”