Year: 2026
Type: article
Abstract: 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.
DOI: 10.1021/jacs.6c03327
Institution: Ruhr University Bochum
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7155075391