Synthetic
organic electrosynthesis has grown in the past few decades
by achieving many valuable transformations for synthetic chemists.
Although electrocatalysis has been popular for improving selectivity
and efficiency in a wide variety of energy-related applications, in
the last two decades, there has been much interest in electrocatalysis
to develop conceptually novel transformations, selective functionalization,
and sustainable reactions. This review discusses recent advances in
the combination of electrochemistry and homogeneous transition-metal
catalysis for organic synthesis. The enabling transformations, synthetic
applications, and mechanistic studies are presented alongside advantages
as well as future directions to address the challenges of metal-catalyzed
electrosynthesis.
Identification of new reactions expands our knowledge of chemical reactivity and enables new synthetic applications. Accelerating the pace of this discovery process remains challenging. We describe a highly effective and simple platform for screening a large number of potential chemical reactions in order to discover and optimize previously unknown catalytic transformations thereby revealing new chemical reactivity. Our strategy is based on labeling one of the reactants with a polyaromatic chemical tag, which selectively undergoes photoionization-desorption process upon laser irradiation without the assistance of an external matrix and enables rapid mass spectrometric detection of any products originating from such labeled reactants in complex reaction mixtures without any chromatographic separation. This method was successfully employed for high-throughput discovery and subsequent optimization of two previously unknown benzannulation reactions.
Multi-component reactions have been extensively employed in many areas of organic chemistry. Despite significant progress, the discovery of such enabling transformations remains challenging. Here, we present the development of a parallel, label-free reaction-discovery platform, which can be used for identification of new multi-component transformations. Our approach is based on the parallel mass spectrometric screening of interfacial chemical reactions on arrays of self-assembled monolayers. This strategy enabled the identification of a simple organic phosphine that can catalyze a previously unknown condensation of siloxy alkynes, aldehydes and amines to produce 3-hydroxy amides with high efficiency and diastereoselectivity. The reaction was further optimized using solution phase methods.
Palladium(II)-catalyzed C-H carbonylation reactions of methylene C-H bonds in secondary aliphatic amines lead to the formation of trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C-H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields for the β-lactam products.
The development of electrochemical catalytic conversion of 5‐hydroxymethylfurfural (HMF) has recently gained attention as a potentially scalable approach for both oxidation and reduction processes yielding value‐added products. While the possibility of electrocatalytic HMF transformations has been demonstrated, this growing research area is in its initial stages. Additionally, its practical applications remain limited due to low catalytic activity and product selectivity. Understanding the catalytic processes and design of electrocatalysts are important in achieving a selective and complete conversion into the desired highly valuable products. In this Minireview, an overview of the most recent status, advances, and challenges of oxidation and reduction processes of HMF was provided. Discussion and summary of voltammetric studies and important reaction factors (e. g., catalyst type, electrode material) were included. Finally, biocatalysts (e. g., enzymes, whole cells) were introduced for HMF modification, and future opportunities to combine biocatalysts with electrochemical methods for the production of high‐value chemicals from HMF were discussed.
Electrochemistry has made a significant impact on scientific discovery and industrial development throughout recent history. One of the most important contributions of the field, the battery, has provided much of the energy storage for this progress. Recently, redox flow batteries have emerged as a promising modern battery technology toward grid‐scale energy storage. Through the employment of non‐aqueous electrolytes and optimization of redox‐active organic molecules as catholyte and anolyte, these batteries have the potential to offer affordable, environmentally‐friendly energy storage without sacrificing desirable high energy densities and long cycling lifetimes. These developments are ongoing, and the associated computational tools have expanded the capabilities and scope of redox flow batteries and shown a path toward the eventual commercialization of this technology to continue to provide power to humanity into a bright future.
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