Electrocatalytic Access to Azetidines via Intramolecular Allylic Hydroamination: Scrutinizing Key Oxidation Steps through Electrochemical Kinetic Analysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15360 - 15369

Опубликована: Июль 10, 2023

Azetidines are prominent structural scaffolds in bioactive molecules, medicinal chemistry, and ligand design for transition metals. However, state-of-the-art methods cannot be applied to intramolecular hydroamination of allylic amine derivatives despite their underlying potential as one the most prevalent synthetic precursors azetidines. Herein, we report an electrocatalytic method sulfonamides access azetidines first time. The merger cobalt catalysis electricity enables regioselective generation key carbocationic intermediates, which could directly undergo C-N bond formation. mechanistic investigations including electrochemical kinetic analysis suggest that either catalyst regeneration by nucleophilic cyclization or second oxidation intermediate is involved rate-determining step (RDS) our protocol highlight ability electrochemistry providing ideal means mediate oxidation.

Язык: Английский

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Synthesis, design and development of energetic materials: Quo Vadis?

Chemical Engineering Journal, Год журнала: 2024, Номер 486, С. 150410 - 150410

Опубликована: Март 14, 2024

Язык: Английский

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Mechanisms and Synthetic Strategies in Visible Light‐Driven [2+2]‐Heterocycloadditions

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(8)

Опубликована: Дек. 28, 2022

The synthesis of four membered heterocycles usually requires multi-step procedures and prefunctionalized reactants. A straightforward alternative is the photochemical [2+2]-heterocycloaddition between an alkene a carbonyl derivative, conventionally based on photoexcitation this latter. However, approach limited by absorption profile carbonyl, requiring in most cases use high-energy UV-light, that often results undesired side reactions and/or degradation reaction components. development new milder visible light-driven [2+2]-heterocycloadditions is, therefore, highly desirable. In Review, we highlight relevant achievements promoted light, with particular emphasis involved mechanisms. open challenges will also be discussed, suggesting possible evolutions, stimulating methodological developments field.

Язык: Английский

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Photosensitized [4+2]‐ and [2+2]‐Cycloaddition Reactions of N‐Sulfonylimines

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июль 3, 2023

Abstract The synthesis of polycyclic compounds is high interest due to the prevalence these motifs in drugs and natural products. Herein, we report on stereoselective construction 3D bicyclic scaffolds azetidine derivatives by modulation N ‐sulfonylimines achieve either [4+2]‐ or [2+2]‐cycloaddition reactions. utility method was established further product. Mechanistic studies are also included, which support reaction via Dexter energy transfer.

Язык: Английский

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Radical strain-release photocatalysis for the synthesis of azetidines

Nature Catalysis, Год журнала: 2024, Номер 7(11), С. 1223 - 1231

Опубликована: Авг. 14, 2024

The increasing popularity of four-member rings in drug discovery has prompted the synthetic chemistry community to advance and reinvent old strategies craft these structures. Recently, strain-release concept been used build complex architectures. However, although there are many for accessing small carbocyclic derivatives, synthesis azetidines remains underdeveloped. Here we report a photocatalytic radical strategy densely functionalized from azabicyclo[1.1.0]butanes. protocol operates with an organic photosensitizer, which finely controls key energy-transfer process distinct types sulfonyl imines. intermediates intercepted by azabicyclo[1.1.0]butanes via process, providing access difunctionalized single step. This is revealed combination spectroscopic optical techniques density functional theory calculations. power generality this method illustrated various azetidine targets, including derivatives celecoxib naproxen. Four-membered have become popular motifs discovery, prompting develop more expedite approaches scaffolds. Here, authors

Язык: Английский

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Exploration of Light Mediated Strategies in Four Membered Heterocycle Synthesis

Tetrahedron, Год журнала: 2025, Номер unknown, С. 134493 - 134493

Опубликована: Янв. 1, 2025

Язык: Английский

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Impact of regiochemistry in energetic materials science: a case of (nitratomethyl-1,2,3-triazolyl)furazans

Dalton Transactions, Год журнала: 2023, Номер 52(22), С. 7673 - 7683

Опубликована: Янв. 1, 2023

The preparation of multipurpose high-energy materials for space technologies remains a challenging task and such usually require special precautions fine tunability their functional properties. To unveil new opportunities en route to high-performance energetic materials, novel potential melt-castable explosives plasticizers incorporating (1,2,3-triazolyl)furazan scaffold enriched with nitro nitratomethyl explosophoric functionalities were synthesized. successful implementation the regiodivergent approach enabled regioisomeric (nitratomethyltriazolyl)furazans that possessed significantly different physicochemical properties classifying target as substances or plasticizers. Hirshfeld surface calculations supported by energy framework plots also performed better understand relationship between molecular structure sensitivity. All prepared (1,2,3-triazolyl)furazans show high nitrogen-oxygen contents (76-77%), good experimental densities (up 1.72 g cm-3) positive enthalpies formation (180-318 kJ mol-1) resulting in detonation performances (D = 7.1-8.0 km s-1; P 21-29 GPa). Overall, this work unveils strategies construction balanced various applications.

Язык: Английский

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Navigating Visible‐Light‐Triggered (aza and thia) Paternò‐Büchi Reactions for the Synthesis of Heterocycles

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(21), С. 3556 - 3571

Опубликована: Авг. 2, 2023

Abstract Harnessing visible light to trigger (aza and thia) Paternò‐Büchi reaction injects new vitality into [2+2] photocyclization enable impressive reactivity modes. The popular is one of the most efficient ways synthesize strained four‐membered heterocycles. Recently, visible‐light‐triggered reactions have received considerable attentions as this strategy has overcome some long‐standing challenges, remarkable achievements been made within field. Strained heterocyclics with favorable properties provide a perfect combination stable skeletons for pharmaceutical chemistry intermediates further transformation. In review, we highlight recent advances in an emphasis on mechanism applications. Organization review follows subdivision according type substrate classes.

Язык: Английский

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Advancements in methodologies and techniques for the synthesis of energetic materials: A review

Energetic Materials Frontiers, Год журнала: 2024, Номер unknown

Опубликована: Июнь 1, 2024

Recent years have witnessed significant advancements in methodologies and techniques for the synthesis of energetic materials, which are expected to shape future manufacturing applications. Techniques including continuous flow chemistry, electrochemical synthesis, microwave-assisted biosynthesis been extensively employed pharmaceutical fine chemical industries and, gratifyingly, found broader This review comprehensively introduces recent utilization these emerging techniques, aiming provide a catalyst development novel green methods synthesizing materials.

Язык: Английский

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Overcoming the Ring Tension: Computational Approaches to Stereochemical Assignments and Geometrical Insights in Small Heterocycles

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер 23(10), С. 2480 - 2490

Опубликована: Янв. 1, 2025

In this study, we evaluate the performance of DP4+ and MM-DP4+ methods on molecules featuring small heterocyclic rings. A dataset 71 containing three- four-membered heterocycles, known for their stereochemical assignment challenges, was analyzed. We compared molecular geometries optimized at different computational levels, including MMFF B3LYP/6-31G*, to assess deviations in key geometric parameters relative heterocycle structures. Furthermore, properties these were investigated using various force fields differences. Our aim reliability B3LYP/6-31G* comparison with more accurate elucidate how influence precision.

Язык: Английский

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