Articles in 2021

Catalytic methods for asymmetric functionalization of unactivated propargylic C–H bonds are scarce. Now, the design of a special ligand for cooperative gold catalysis enables the intramolecular, enantioselective addition of propargylic C–H bonds to aldehyde groups providing chiral cyclopentane/cyclohexane-fused homopropargylic alcohols.

Asymmetric dioxygenation of alkenes is an attractive concept to synthesize enantioenriched diols, but the performance in the case of terminal alkenes is low with current methods. Now, this has been addressed by an asymmetric oxypalladation process that provides access to enantioenriched 1,2-diols, enabled by the chiral 6-modified pyridinyl oxazoline ligand.

Tracking immobilized molecular complexes under in situ conditions is vital for the development of next-generation catalysts, although the poor surface sensitivity of many techniques makes this challenging. Now, the role of the anchoring group in a nickel bis(terpyridine) complex has been elucidated by in situ gap-plasmon-assisted SERS coupled with DFT calculations.

Understanding the structure–property relationships of metal-exchanged zeolites is a challenging task. Here, correlations are established between the adsorption properties of Cu-exchanged ZSM5 and the reaction kinetics of NO decomposition, generating descriptors of general applicability to different zeolites.

Mechanistic details of Ni-catalysed functionalizations of strong sigma C–O bonds in synthetic chemistry have been elusive. Now, the identification and characterization of important Ni species, as well as the role of a ZnCl₂ additive and solvent in the coupling of aryl esters, are reported.

Single-atom catalysts can exhibit improved catalytic performance with respect to their bulk counterparts. Now, the authors introduce a yolk@shell catalyst with spatially separated Pd and Fe single sites that simultaneously catalyse nitroaromatic hydrogenation and alkene epoxidation reactions, leading to a cascade synthesis of amino alcohols.

The coupling of aryl halides and arylboronic acids is generally performed by metal-catalysed Suzuki–Miyaura reactions while metal-free approaches remain elusive. Here an organocatalytic approach based on amine catalysts is introduced for the preparation of commercially relevant asymmetric biaryls.

Multi-element oxide catalysts can feature superior properties compared with their single-element analogues but obtaining such complex structures remains a challenge. Here, a method is reported to access single-phase denary nanoparticles as stable and efficient catalysts for the combustion of methane.

As Ni(ii) complexes are generally considered inert toward O₂, their utilization for catalytic oxygenation reactions is extremely rare. Here, the authors introduce an electrocatalytic method for the oxidation of sulfides based on bipyridine complexes of simple Ni(ii) salts using water as the oxygen source.

Biological CO₂ fixation is restricted to few enzymes and pathways, limiting its value in environmental protection and agricultural productivity. Now, a new-to-nature CO₂-fixing enzyme allows CO₂-dependent assimilation of glycolate in a designed pathway, and its use for different applications is demonstrated.

General methods to regioselectively introduce both amine and alcohol functionalities into alkene substrates to afford 1,2-aminoalcohols in a single step are lacking. Now, this has been addressed by a metal-free photosensitization strategy using oxime carbonate as a suitable bifunctional reagent.

Biocatalytic methods are lacking in current computer-aided synthesis planning tools. Now, RetroBioCat allows computer-aided design of biocatalytic cascades for organic synthesis and synthetic biology. The program was validated using reported cascades and is freely available at retrobiocat.com.