Organic & Biomolecular Chemistry最新文献

Chirality has become a fundamental design principle to craft peptide materials. In contrast, the systematic exploitation of chirality to build glycan materials remains largely unexplored, despite the rich chiral diversity of carbohydrates, with both D- and L-configurations readily available in nature. Here, we emphasize the added value of exploring mirror-image glycans to tailor carbohydrate materials. By examining the distinctive chiral features of carbohydrates in comparison to peptides, we demonstrate how these characteristics provide powerful opportunities to modulate and elucidate the rules governing glycan assembly. We discuss examples of carbohydrate materials based on individual enantiomers, the co-assembly of racemic mixtures, and the assembly of heterochiral sequences. Each section is introduced with key insights from peptide materials, serving as inspiration and guidance for the future design of glycan assemblies.

In summary, a novel spirocyclisation approach based on the oxidative nucleophilic addition of amide enolates to π-deficient aromatic rings was developed. This protocol allowed the preparation of complex and diverse heterocyclic bis-lactam scaffolds, which proved to be valuable cores for medicinal chemistry applications. Several spirocyclic inhibitors of PRMT5 were thus prepared, with the spirocyclisation tolerating diverse substituents, allowing tuning of biological activity as well as modulation of physicochemical properties.

The development of efficient synthetic methods for α-boryl ureas is of significant interest due to their potential as drug-like scaffolds in medicinal chemistry. Herein, we present a multicomponent strategy that transforms α-haloboronates, trimethylsilyl isocyanate, sodium iodide, and amines into diverse drug-like scaffold α-boryl ureas under mild conditions. This protocol features broad substrate scope and great functional-group tolerance, and enables the regioselective synthesis of previously inaccessible α-boryl ureas, including late-stage functionalization of drug molecules. Mechanistic studies suggest that a regioselective 1,2-boronate migration pathway may underlie the different regioselectivities observed with primary and secondary amines. To highlight the potential of this methodology in drug discovery, an α-boryl urea analog of nirmatrelvir was synthesized, exhibiting remarkable inhibitory activity (IC₅₀ = 12 nM) against the SARS-CoV-2 main protease. This work not only provides a streamlined and practical synthetic route to diverse α-boryl ureas, but also underscores their potential as valuable scaffolds in the development of new therapeutics.

N-Arylsulfonamides are key scaffolds in pharmaceuticals and agrochemicals. Herein, a copper-catalyzed N–S bond coupling between hydroxylamines and sulfinic acids that enables the direct synthesis of N-arylsulfonamides without additional oxidants has been demonstrated. The protocol features the advantages of operational simplicity, environmental friendliness and mild reaction conditions. Mechanistic studies have shown that hydroxylamine exhibits unique multifunctionality in this reaction, serving as a reducing reagent, an amine donor, and a potential oxidant.

We report a gold-catalysed cyclisation of N-allenamides derived from 1- and 2-(2-aminoaryl)indoles, providing easy access to 5,6-dihydroindolo[1,2-a]quinoxalines and 6,11-dihydro-5H-indolo[3,2-c]quinolines. The reaction proceeds under mild conditions, tolerates diverse functional groups, and enables the synthesis of previously unexplored indole-fused heterocycles, whose versatility was demonstrated through selected post-functionalisation reactions.

An effective method for constructing thermodynamically unstable 1Z,4Z-dienes via Rh-catalysed cross-coupling of allylic gem-difluorides with tertiary Z-allylic alcohols has been developed. The fluoride elimination of the gem-difluoride propenes and β-Z-alkenyl elimination of the tertiary Z-allylic alcohols have been combined smoothly. This transformation furnishes a series of fluorinated (1Z,4Z)-dienes in moderate-to-high yields under mild conditions, exhibiting broad substrate scope, excellent functional group tolerance, and excellent chemo- and regioselectivity.

Expression of Concern for ‘Total synthesis of the natural product EBC-329’ by Raju S. Thombal and Vrushali H. Jadhav, Org. Biomol. Chem., 2015, 13, 9485–9491, https://doi.org/10.1039/C5OB01276G.

A rare strategy for three-component tandem benzyl-C(sp³)-H functionalization via thermally generated arynes with phenazine without a catalyst was developed for the first time. A series of novel fused N,N'-disubstituted dihydrophenazine derivatives were synthesized with excellent yield and high atomic utilization. Deuterium-labelling studies suggested that the formation of carboanion intermediates has a significant role in the reaction. Our data enrich the field of C(sp³)-H functionalization and promote the development of aryne chemistry.

In the past decade, 4-chloro-2H-chromene-3-carbaldehyde scaffolds (CCCS) have emerged as versatile precursors in modern organic synthesis. This review critically analyzes recent advancements in the chemical reactivity and synthetic accessibility of CCCS. We evaluate their pivotal role in developing potent agents against inflammation, cancer, and microbial resistance, while also addressing applications in energy sectors. By identifying the most efficient derivatives within each series, this work provides a strategic framework for leveraging CCCS in future pharmaceutical and materials science research.

Correction for ‘Asymmetric synthesis of isoindolines via a palladium-catalyzed enantioselective intramolecular oxidative aminoacetoxylation reaction’ by Dongyuan Ju et al., Org. Biomol. Chem., 2025, https://doi.org/10.1039/d5ob01595b.