Redox transformations are of fundamental importance to organic chemistry and are the basis for converting hydrocarbon feedstocks to value added, densely functionalized pharmaceuticals, agrochemicals, or materials. This talk will explore two distinct areas of redox chemistry.

First, I will present our work on oxoammonium catalysts for diol desymmetrization and C–H oxidation of N-substituted amines and ethers via a hydride-abstraction mechanism. Using a novel class of highly modular chiral oxoammonium-peptides and a generality-oriented optimization approach screening catalysts across a diverse panel of substrates, we established broadly applicable conditions for oxidative meso-diol and pyrrolidine desymmetrization. Building on this rich catalyst-substrate structure–reactivity data, our mechanistic studies revealed key relationships governing oxoammonium-mediated hydride transfer and asymmetric induction.

Second, I will highlight our development of two now commercial platforms that unlock microscale high-throughput experimentation for electrosynthesis. The HTe^-Chem is a standardized 24-well plate and uses a wired electrochemical circuit, enabling sub-mL electrolyses under virtually any electrolysis condition. To further miniaturize and make electrochemistry more accessible, we developed SPECS: Microelectronic devices that convert red light into electricity using on-board photovoltaics, transforming any standard 96/384-well plate into an array of wireless electrochemical reactors. SPECS enable µL-scale electrosynthesis across a broad range of literature reactions, accelerate optimization and library synthesis, and have facilitated the discovery of a sulfilimine synthesis via oxidative S–N coupling.

Jonas Rein

Massachusetts Institute of Technology

Appearances