Homogeneous catalysis articles from across Nature Portfolio

Installation of small aliphatic motifs within pharmaceuticals provides a medicinally relevant tool in drug discovery programmes. Here, the authors report a late-stage meta-C–H alkylation method facilitating the biological properties modulation of therapeutic agents.

Palladium-catalysed C(sp³)–H amination reactions of carboxylic acids are challenging due to N-coordination often outcompeting the carboxylic acid directing effect. Now, the development of chlorinated pyridine–pyridone ligands for palladium-catalysed methylene C(sp³)–H lactamization and cycloamination is reported, enabling the synthesis of lactams and cyclic amines.

Cross-dehydrogenative coupling (CDC) of C-H bonds is an ideal approach for C-C bond construction but suffers from low selectivity of similar C-H bonds. Here, the authors describe a highly selective paired electrocatalysis strategy towards CDC combining hydrogen evolution reaction catalysis with hydride transfer catalysis.

Individual metal atoms and few-atom metal clusters have shown promising catalytic activities, however, their exploitation in the total synthesis of complex organic molecules remains underexplored. Here, the authors develop a total synthesis of the bioactive natural product (±)-Licarin B involving key steps catalyzed by soluble individual Pd atoms and Cu/Pd/Pt clusters, achieving an 11-step linear synthesis and overall yield of 13.1%.

Despite the widespread utility of ruthenium catalysts, many protocols for their use require high temperatures or light irradiation. Now, the synthesis of an air- and moisture-stable ruthenium precatalyst has been reported. This versatile catalyst drives an array of transformations and enables rapid screening and optimization of reactions, revealing previously unknown in situ generated ruthenium complexes.

Controlling regioselectivity is one of the most challenging aspects for the construction of aryl boron compounds, and there are few practical and general strategies for such transformations. Here, the authors report an iridium-catalyzed trialkoxysilane protecting group-assisted regioselective C–H borylation with various aromatic compounds.

A method for carbon isotope exchange involving a metal-catalysed metathesis reaction of in situ formed acyl chlorides is demonstrated. The platform provides access to ¹³C- or ¹⁴C-enriched carboxylic acids, including natural products and pharmaceuticals, without the need for radioactive gases, using a single carboxylic acid carbon donor.

Conformational dynamics are integral to enzyme catalysis, yet they are barely explored when designing synthetic catalysts. Now, a catenane-based organocatalyst, which dynamically switches between two conformations, speeds up the catalysis of carbodiimide hydration through spontaneous conformational adaptation for different reaction steps.

Fluoroalkyl fragments are ubiquitous motifs in pharmaceuticals and agrochemicals, but their introduction to a given molecule typically involves expensive or difficult-to-handle reagents. Now, the photocatalysed hydrofluoroalkylation of alkenes has been achieved using simple and readily available fluoroalkyl carboxylic acids.

Selective electrochemical oxidation of ammonia provides an ideal pathway to synthesize hydrazine, but this process is outcompeted by a more favourable overoxidation to N₂. A molecular ruthenium catalyst has now flipped the script, circumventing the thermodynamic challenges to selectively generate hydrazine.