The unexpected reactivity and stability limits of phosphorus ylide-based aluminum- and gallium-carbon ambiphiles are described. While the previously published t-butyl-substituted compound (2-{AltBu2}...

The introduction of a single C-atom into organic substrates typically results in the formation of flat molecules containing unsaturated C(sp)-centers. Adding a single C(sp3)-atom surrounded by four σ-...

Precise modification of a chemical site in a molecule at the single-atom level is one of the most elegant yet difficult transformations in chemistry. A reagent specifically designed for chemoselective...

Increasing the donor strength of Lewis bases is a viable strategy to stabilize reactive electron-deficient species. Herein, we utilize the strong electron-releasing power of ylide substituents to gain...

With advances in the applications of earth-abundant organopotassium reagents in C–C bond forming processes, this study pioneers Pd-catalyzed cross coupling reactions between aryl halides and a range of aryl and benzylpotassium species generated by direct C–H metalation. Key for the success of this approach is the use of electron-rich ylide-substituted phosphine (YPhos) ligands, which enable fast conversion of the potassium species in solution. This protocol can be carried out in a one-pot manner at room temperature, without the need for purification of the in situ prepared organopotassium compounds or any additional additives, enabling the isolation of a broad scope of coupling products even on a gram-scale.

The Front Cover shows a sketchpad with the structure of the formal methanol activation product of an aluminum–carbon-based ambiphile that is formed by the elimination of ammonia. A water molecule is ...

The pyridylketene has previously been isolated via matrix isolation and demonstrated potential in the synthesis of N-heterocycles. Herein, we report the synthesis and isolation of the pyridylketenyl anion through conventional synthetic methods, involving metalation and subsequent carbonylation of the readily available 2-pyridyl ylide. Quantum chemical calculations reveal extensive delocalization of the negative charge across the entire molecular framework, resulting in multiple nucleophilic sites that are best described by a series of resonance structures. IR spectroscopic and X-ray diffraction data corroborate this electronic structure, indicating a markedly compressed C–C–C–O moiety. The pronounced charge delocalization enables diverse reactivities and promotes cyclization pathways involving the pyridine nitrogen. Accordingly, the pyridylketenyl anion serves as a versatile precursor for the construction of heterocycles featuring triazolone, quinolizine, and indolizine motifs, underscoring its broad applicability as a building block in heterocycle synthesis.

A reliable and scalable purification procedure for the easy removal of triphenylphosphine oxide by complexation with CaBr2 in ethereal solvents or toluene was developed. The resulting insoluble precip...

Communications Chemistry, Published online: 03 December 2025; doi:10.1038/s42004-025-01701-0Understanding cycloaddition mechanisms is beneficial for the creation of extended carbon nanostructures, yet traditional models often overlook symmetry-based mechanistic effects. Here, the authors employ topological classifiers to identify symmetry-forbidden pathways in polycyclic aromatic azomethine ylide cycloadditions, revealing that topologically-allowed endothermic reactions can guide nanographene engineering.

A pyridinium ylide-alkylation strategy has been developed for selectively accessing N,N-disubstituted pyridinium salts from monosubstituted pyridinium salts possessing ambident nucleophiles. The metho...