New horizons in organic chemistry: ICIQ advances single-carbon insertion for C−C bond editing

Researchers from the group of Prof. Marcos Garcia Suero, from the Institute of Chemical Research of Catalonia (ICIQ), have developed a novel single-carbon insertion into single C−C bonds using diazirines as arylchlorocarbene precursors. The single-carbon insertion occurs with the creation of an alkene and can formally be seen as a cationic carbyne transfer into single C−C bonds.

The group aimed to develop a novel single-carbon insertion into single C−C bonds with reactive equivalents of cationic carbynes or carbynoids with dual carbene/carbocation behaviour. In this work, presented in the Journal of the American Chemical Society (JACS), the authors have reported the successful development of this concept by using diazirines as precursors of chloroarylcarbenes, which act as carbynoid species capable of functionalizing tertiary C−H bonds with excellent site selectivity. This article has been highlighted as Highly-accessed for the journal.

“This work represents a significant step forward in skeletal editing, demonstrating the potential of diazirines as versatile tools for single-carbon insertions into C−C bonds. This strategy highlights the utility of chloroarylcarbenes as cationic carbyne equivalents in enabling molecular modifications with high precision, offering a valuable tool for exploring new chemical spaces relevant to various industries.” explains Prof. Marcos Garcia Suero.

Skeletal editing processes that selectively delete, insert or exchange an atom in the skeleton of organic molecules have recently gained considerable momentum. Such processes and synthetic strategies are of significant interest to the pharmaceutical, agrochemical, perfumery and material industries due to their retrosynthetic simplicity and ability to diversify organic molecules at the skeletal level, giving access to a chemical space difficult or impossible to reach through conventional strategies.

The work presented here is part of Prof. Suero’s ERC Consolidator grant “CARBYNE: New carbon reactivity rules for molecular editing”. The EU-funded CARBYNE project is developing novel catalytic pathways to produce carbyne equivalents and related species to enhance applications of these unique and promising carbon reactive species in numerous fields.

Reference publication

Single-Carbon Insertion into Single C-C Bonds with Diazirines
Alfonso, V. G.; de la Vega-Hernández, K.; Suero, M. G.;
J. Am. Chem. Soc. 2025, 147, 1, 57–62
DOI: 10.1021/jacs.4c12632