Asymmetric pallada‐electrocatalyzed C−H olefinations were achieved through the synergistic cooperation with transient directing groups. The electrochemical, atroposelective C−H activations were realized with high position‐, diastereo‐, and enantio‐control under mild reaction conditions to obtain highly enantiomerically‐enriched biaryls and fluorinated N−C axially chiral scaffolds. Our strategy provided expedient access to, among others, novel chiral BINOLs, dicarboxylic acids and helicenes of value to asymmetric catalysis. Mechanistic studies by experiments and computation provided key insights into the catalyst's mode of action.

A new method for the direct conversion of 4-pentenylsulfonamides to 2-formylpyrrolidines and a 2-ketopyrrolidine has been developed. This transformation occurs via aerobic copper-catalyzed alkene aminooxygenation where molecular oxygen serves as both oxidant and oxygen source. The 2-formylpyrrolidines can further undergo oxidative carbon–carbon bond cleavage in situ upon addition of DABCO, providing 2-pyrrolidinones. These transformations have been demonstrated for a range of 4-pentenylsulfonamides. 4-Pentenylalcohols also undergo oxidative cyclization to form γ-lactones predominantly. The reaction is chemoselective, oxidizing one alkene in the presence of others, and is compatible with several functional groups. Application of these reactions to the formal syntheses of baclofen and (+)-monomorine was demonstrated.

Enantioselective palladaelectro-catalyzed C–H alkenylations and allylations were achieved by the means of an easily-accessible amino acid for the synthesis of N–C axially chiral indole biaryls.

A system for transfer hydrogenation of alkenes, composed of a ruthenium metathesis catalyst and HCOOH, is presented. This operationally simple system can be formed directly after a metathesis reaction to effect hydrogenation of the metathesis product in a single-pot. These hydrogenation conditions are applicable to a wide range of alkenes and offer remarkable selectivity.

Cobalt not only is an essential micronutrient for mammals but also marks itself as important in organic synthesis, especially in the field of catalysis. Various useful reactions, such as alkene hydroformylation, hydrogenation, heterofunctionalizations of carbon−carbon double bonds, C−H activation, and crosscoupling reactions, have been realized with the aid of this metal. At the same time, cobalt deserves special attention as a catalyst for radical processes; in fact, in the form of vitamin B 12 , it was designed by Nature as a reversible carrier for radicals. Since this molecule is a native Co-complex, it is very attractive for the development of sustainable transformations, and it has already been demonstrated that vitamin B 12 and its derivatives mediate numerous reactions that have found applications in both the construction of complex molecules and the degradation of polyhalogenated pollutants. However, in this Perspective, we focus the readers' attention on radical C−C bond forming reactions catalyzed by vitamin B 12 , which are particularly important as a tool for the synthesis of important molecules in a greener manner. We also ponder over the challenges that remain to be addressed and the solutions that are expected to come.

Red-light enables deeper material penetration, which is important for biological applications and has consequences for chemical synthesis. Therefore, the search for new photocatalysts that absorb in this region is crucial. Despite the undeniable utility of porphyrins in blue-and green-light-induced energy-and electron-transfer processes, they are also perfectly suited for redlight applications. Herein, we describe free-base porphyrins as photoredox catalysts for red-light-induced organic transformations. They can act as both photooxidants and photoreductants and can accomplish the synthesis of biaryls once merged with Pd-catalysis. The developed methodology holds promise for broader applications, as the heme-based protoporphyrin is used as a photocatalyst and reactions can be realized in aqueous conditions.

Reduction of waste is an important goal of modern organic synthesis. We report herein oxidase reactivity for enantioselective intramolecular copper-catalyzed alkene carboamination and carboetherification reactions where previously used stoichiometric MnO2 has been replaced with oxygen. This substitution was risky as the reaction mechanism is thought to involve C–C bond formation via addition of alkyl carbon radicals to arenes. Such intermediates are also susceptible to C–O bond formation via O2 addition. Control of absolute stereochemistry under aerobic conditions was also uncertain. The oxidative cyclization efficiencies appear to track with the ease of the radical addition to the arenes.

Novel ruthenium(II) complexes were obtained as a result of a stoichiometric reaction of Grubbs' benzylidene second generation catalysts with 3-nitropropene. These stable complexes, formally ruthenaisoxazole N-oxide derivatives, display activity in both metathesis and non-metathetic processes such as cycloisomerisation, isomerisation and transfer hydrogenation.