Organic Electrochemistry: Molecular Syntheses with Potential.

Efficient and selective molecular syntheses are paramount to inter alia biomolecular chemistry and material sciences as well as for practitioners in chemical, agrochemical, and pharmaceutical industries. Organic electrosynthesis has undergone a considerable renaissance and has thus in recent years emerged as an increasingly viable platform for the sustainable molecular assembly. In stark contrast to early strategies by innate reactivity, electrochemistry was recently merged with modern concepts of organic synthesis, such as transition-metal-catalyzed transformations for inter alia C-H functionalization and asymmetric catalysis. Herein, we highlight the unique potential of organic electrosynthesis for sustainable synthesis and catalysis, showcasing key aspects of exceptional selectivities, the synergism with photocatalysis, or dual electrocatalysis, and novel mechanisms in metallaelectrocatalysis until February of 2021.

Electroreductive Nickel-Catalyzed Thiolation: Efficient Cross-Electrophile Coupling for C-S Formation.

Sulfur-containing molecules are of utmost topical importance towards the effective development of pharmaceuticals and functional materials. Herein, we present an efficient and mild electrochemical thiolation by cross-electrophile coupling of alkyl bromides with functionalized bench-stable thiosulfonates to access alkyl sulfides with excellent efficacy and broad functional group tolerance. Cyclic voltammetry and potentiostatic analysis were performed to elucidate mechanistic insights into this electrocatalytic thiolation reaction.

Electroreductive Cobalt-Catalyzed Carboxylation: Cross-Electrophile Electrocoupling with Atmospheric CO2.

The chemical use of CO2 as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carboxylations of allylic chlorides with CO2 . Styrylacetic acid derivatives were obtained with moderate to good yields and good functional group tolerance. The thus-obtained products are useful as versatile synthons of γ-arylbutyrolactones. Cyclic voltammetry and in operando kinetic analysis were performed to provide mechanistic insights into the electrocatalytic carboxylation with CO2 .