Oxidative amination of unactivated alkenes via nitrogen atom insertion into carbon-carbon double bonds DOI Creative Commons
Yannick Brägger, Ann-Sophie K. Paschke, Nima Nasiri

et al.

Published: May 20, 2024

The synthesis of nitrogen-containing molecules through C–N bond formation is critical for the discovery and preparation medicines, agrochemicals materials. Traditional synthetic methods using alkenes as ubiquitous substrates leverage reactivity C(sp2)–C(sp2) π formation. In contrast, that can form bonds complete cleavage double are scarce, despite considerable potential such a strategy. Here, we report direct insertion nitrogen atom into unactivated carbon-carbon to access aza-allenium intermediates which be converted either nitriles or amidine products, depending on initial alkene substitution pattern. This operationally simple highly functional group tolerant reaction works wide range alkenes. Our mechanistic proposal supported by chemical trapping experiments, concomitantly demonstrate utility our method valuable N-heterocycles. Overall, this study demonstrates possibility reactive (i.e. aza-alleniums), have ample downstream diversification, from alkenes, opening new avenues important products.

Language: Английский

Molecular Ring Remodeling through C–C Bond Cleavage DOI
Zengrui Cheng, Zhibin Hu, Ning Jiao

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

ConspectusStable and inert C-C bonds form the fundamental framework of organic compounds. Consequently, direct transformations involving bond cleavage present an innovative approach for rapid modification remodeling molecular skeletons. In recent years, concept skeletal editing has garnered widespread attention been significantly developed, providing new opportunities late-stage bioactive molecules, high-value transformation bulk chemicals, a revolution in traditional fragment coupling strategies chemical synthesis. Notable advancements this field have focused on cyclic including ring expansion, contraction, ring-opening reactions, thereby enriching synthetic toolbox available to chemists. However, selective remains formidable challenge, especially complex due high dissociation energy difficulty achieving precise selectivity control. Over past few our group made efforts address these challenges. We demonstrated potential molecule reactions as efficient strategy synthesis molecules.Herein, we two major thematic achieved by group, utilizing cascade activation entropy-driven reconstruction via cleavage. These are characterized mild conditions, accessibility catalysts reagents, exceptional functional compatibility, emerging novel approaches through atom-incorporation mainly nitrogenation, oxygenation, halogenation synthesize pharmaceuticals, natural products, material molecules. (1) Ring expansion reactions: developed that enable insertion C-, N-, O-containing units into rings. methodologies offer practical routes synthesizing amides, amines, lactones, nitrogen-containing heterocycles. (2) Ring-opening enables construction distally difunctionalized frameworks. By transition metal catalysis radical-mediated process, successfully both single C═C double within Furthermore, tackled highly challenging arene (ARO) reaction, enabling stereoselective conjugated systems unsaturation liberation aromatic systems. Mechanistic studies DFT calculations provided critical insights processes. also identified key intermediates involved cleavage, benzyl azide, O-acetyl hydroxylamine, β-azido peroxyl radical, copper bisnitrene, 2-nitrene indazole. findings deepened understanding mechanisms strategy, which further promoted discovery related acyclic substrates.

Language: Английский

Citations

0
Oxidative amination of unactivated alkenes via nitrogen atom insertion into carbon-carbon double bonds DOI Creative Commons
Yannick Brägger, Ann-Sophie K. Paschke, Nima Nasiri

et al.

Published: May 20, 2024

The synthesis of nitrogen-containing molecules through C–N bond formation is critical for the discovery and preparation medicines, agrochemicals materials. Traditional synthetic methods using alkenes as ubiquitous substrates leverage reactivity C(sp2)–C(sp2) π formation. In contrast, that can form bonds complete cleavage double are scarce, despite considerable potential such a strategy. Here, we report direct insertion nitrogen atom into unactivated carbon-carbon to access aza-allenium intermediates which be converted either nitriles or amidine products, depending on initial alkene substitution pattern. This operationally simple highly functional group tolerant reaction works wide range alkenes. Our mechanistic proposal supported by chemical trapping experiments, concomitantly demonstrate utility our method valuable N-heterocycles. Overall, this study demonstrates possibility reactive (i.e. aza-alleniums), have ample downstream diversification, from alkenes, opening new avenues important products.

Language: Английский

Citations

2