An efficient reaction at the counter electrode is of key importance for the success of net oxidative and net reductive electrochemical transformations. For electrooxidative processes, cathodic proton reduction to H 2 serves as the benchmark counter reaction. In contrast, net reductive electrochemical transformations have less attractive oxidative counter reactions to choose from and commonly rely on dissolution of a sacrificial anode that effectively results in stoichiometric metal consumption for the processes. In this study, we demonstrate that anodic borohydride oxidation has great potential to successfully replace the use of such sacrificial anodes for a variety of electroreductive organic transformations. This anodic transformation effectively serves as the inverse of cathodic proton reduction, producing H 2 using inert carbon‐based electrode materials.

Titanium is an earth abundant metal with low toxicity that is able to form complexes that mediate a wide range of organic transformations in both polar and radical manifolds. In context of the latter, the use of Ti-catalysts in electrosynthesis is surprisingly underexplored, considering the great potential for electrochemical (re)generation of low-valent and catalytically active species. To spur further innovation in the field, this Review provides an overview of the current literature and discusses the limitations and possibilities for electrochemically driven Ti-catalysis.

Herein, we present an electrochemical desulfurative protocol for the formation of alkyl boronic esters from thioethers. The paired electrolytic transformation utilizes HBpin as coupling partner and proceeds with inert electrodes. The transformation features mild conditions, broad substrate scope and excellent functional group tolerance, as illustrated by late-stage functionalization of pharmaceutical compounds and natural products. Furthermore, the protocol is scalable, successfully producing gram quantities of borylated product.

Chiral and enantiopure perfluorinated sulfonimidamides act as low-molecular weight gelators at low critical gelation concentration (<1 mg mL-1) via supramolecular polymerization in nonpolar organic solvents and more heterogenic mixtures, such as biodiesel and oil. Freeze-drying of the organogel leads to ultralight aerogel with extremely low density (1 mg mL-1). The gelation is driven by hydrogen bonding resulting in a helical molecular ordering and unique fibre assemblies as confirmed by scanning electron microscopy, CD spectroscopy, and computational modeling of the supramolecular structure.

Thioethers are highly prevalent functional groups in organic compounds of natural and synthetic origin but remain remarkably underexplored as starting materials in desulfurative transformations. As such, new synthetic methods are highly desirable to unlock the potential of the compound class. In this vein, electrochemistry is an ideal tool to enable new reactivity and selectivity under mild conditions. Herein, we demonstrate the efficient use of aryl alkyl thioethers as alkyl radical precursors in electroreductive transformations, along with mechanistic details. The transformations proceed with complete selectivity for C(sp3)−S bond cleavage, orthogonal to that of established transition metal-catalyzed two-electron routes. We showcase a hydrodesulfurization protocol with broad functional group tolerance, the first example of desulfurative C(sp3)−C(sp3) bond formation in Giese-type cross-coupling and the first protocol for electrocarboxylation of synthetic relevance with thioethers as starting materials. Finally, the compound class is shown to outcompete their well-established sulfone analogues as alkyl radical precursors, demonstrating their synthetic potential for future desulfurative transformations in a one-electron manifold.

Sulfonimidamides (SIAs) and sulfoximines (SOIs) have attracted attention due to their potential in agriculture and in medicinal chemistry as bioisosteres of biologically active compounds, and new synthetic methods are needed to access and explore these compounds. Herein, we present a light-promoted generation of perfluorinated aromatic nitrenes, from perfluorinated azides, that subsequently are allowed to react with sulfinamides and sulfoxides, generating achiral and chiral SIAs and SOIs. One of the enantiopure SIAs was evaluated as a novel chiral auxiliary in Grignard additions to the imines yielding the product in up to 96:4 diastereomeric ratio.

Sulfonimidamides and sulfoximines have attractedattention due to their potential in agriculture and in medicinalchemistry as bioisosteres to biologically active compounds. Therefore,novel synthetic methods are needed to access new chemical spaceof these compounds. Herein, we present a light-promoted generationof perfluorinated aromatic nitrenes, from perfluorinated azides, thatsubsequently are allowed to react with sulfinamides and sulfoxides,generating achiral and chiral sulfonimidamides and sulfoximines. Oneof the novel chiral sulfonimidamides were evaluated as a chiralauxiliary in Grignard additions to the imines yielding the correspondingamine products in up to 95:5 diastereomeric ratio.