Light-harvesting microelectronic devices for wireless electrosynthesis.

High-throughput experimentation (HTE) has accelerated academic and industrial chemical research in reaction development and drug discovery and has been broadly applied in many domains of organic chemistry. However, application of HTE in electrosynthesis-an enabling tool for chemical synthesis-has been limited by a dearth of suitable standardized reactors. Here we report the development of microelectronic devices, which are produced using standard nanofabrication techniques, to enable wireless electrosynthesis on the microlitre scale.

Oxoammonium-Catalyzed Oxidation of -Substituted Amines.

We report the development of oxoammonium-catalyzed oxidation of -substituted amines via a hydride transfer mechanism. Steric and electronic tuning of catalyst led to complementary sets of conditions that can oxidize a broad scope of carbamates, sulfonamides, ureas, and amides into the corresponding imides. The reaction was further demonstrated on a 100-g scale using a continuous flow setup.

Oxoammonium-Catalyzed Ether Oxidation via Hydride Abstraction: Methodology Development and Mechanistic Investigation Using Paramagnetic Relaxation Enhancement NMR.

Hydride abstraction represents a promising yet underexplored approach in the functionalization of C-H bonds. In this work, we report the oxidation of α-C-H bonds of ethers via oxoammonium catalysis using 3-chloroperbenzoic acid (CPBA) as the terminal chemical oxidant or by means of electrochemistry. Mechanistic studies revealed intricate equilibria and interconversion events between various catalytic intermediates in the presence of CPBA, which alone however was incompetent to drive catalytic turnover.

Correction: A tutorial on asymmetric electrocatalysis.

Correction for 'A tutorial on asymmetric electrocatalysis' by Jonas Rein , , 2023, https://doi.org/10.1039/D3CS00511A.

A tutorial on asymmetric electrocatalysis.

Electrochemistry has emerged as a powerful means to enable redox transformations in modern chemical synthesis. This tutorial review delves into the unique advantages of electrochemistry in the context of asymmetric catalysis. While electrochemistry has historically been used as a green and mild alternative for established enantioselective transformations, in recent years asymmetric electrocatalysis has been increasingly employed in the discovery of novel asymmetric methodologies based on reaction mechanisms unique to electrochemistry.

A Physical Organic Approach towards Statistical Modeling of Tetrazole and Azide Decomposition.

Nitrogen atom-rich heterocycles and organic azides have found extensive use in many sectors of modern chemistry from drug discovery to energetic materials. The prediction and understanding of their energetic properties are thus key to the safe and effective application of these compounds. In this work, we disclose the use of multivariate linear regression modeling for the prediction of the decomposition temperature and impact sensitivity of structurally diverse tetrazoles and organic azides.

Electrochemically driven cross-electrophile coupling of alkyl halides.

Recent research in medicinal chemistry has suggested that there is a correlation between an increase in the fraction of sp carbons-those bonded to four other atoms-in drug candidates and their improved success rate in clinical trials. As such, the development of robust and selective methods for the construction of carbon(sp)-carbon(sp) bonds remains a critical problem in modern organic chemistry. Owing to the broad availability of alkyl halides, their direct cross-coupling-commonly known as cross-electrophile coupling-provides a promising route towards this objective.

Unlocking the Potential of High-Throughput Experimentation for Electrochemistry with a Standardized Microscale Reactor.

Organic electrochemistry has emerged as an enabling and sustainable technology in modern organic synthesis. Despite the recent renaissance of electrosynthesis, the broad adoption of electrochemistry in the synthetic community, and especially in industrial settings, has been hindered by the lack of general, standardized platforms for high-throughput experimentation (HTE). Herein, we disclose the design of the HT Chem, a high-throughput microscale electrochemical reactor that is compatible with existing HTE infrastructure and enables the rapid evaluation of a broad array of electrochemical reaction parameters.

Electrochemical C-H Functionalization of (Hetero)Arenes-Optimized by DoE.

A novel approach towards the activation of different arenes and purines including caffeine and theophylline is presented. The simple, safe and scalable electrochemical synthesis of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) aryl ethers was conducted using an easy electrolysis setup with boron-doped diamond (BDD) electrodes. Good yields up to 59 % were achieved.