Carbon–nitrogen transmutation in polycyclic arenol skeletons to access N-heteroarenes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 4, 2024

Abstract Developing skeletal editing tools is not a trivial task, and realizing the corresponding single-atom transmutation in ring system without altering size even more challenging. Here, we introduce strategy that enables polycyclic arenols, highly prevalent motif bioactive molecules, to be readily converted into N -heteroarenes through carbon–nitrogen transmutation. The reaction features selective nitrogen insertion C–C bond of arenol frameworks by azidative dearomatization aryl migration, followed ring-opening, ring-closing (ANRORC) achieve carbon-to-nitrogen aromatic framework arenol. Using widely available arenols as -heteroarene precursors, this alternative approach allows streamlined assembly complex heteroaromatics with broad functional group tolerance. Finally, pertinent transformations products, including synthesis biheteroarene skeletons, were conducted exhibited significant potential materials chemistry.

Language: Английский

---

Precision single-atom editing: new frontiers in nitrogen insertion and substitution for the generation of N-heterocycles

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4041 - 4053

Published: Jan. 1, 2024

This paper primarily focuses on the editing of nitrogen atoms, encompassing insertion N, substitution C with and utilization 15 N in place 14 for construction N-heterocycles.

Language: Английский

---

Synthesis of naphthalene derivatives via nitrogen-to-carbon transmutation of isoquinolines

Science Advances, Journal Year: 2025, Volume and Issue: 11(5)

Published: Jan. 29, 2025

Heteroarene skeletal editing is gaining popularity in synthetic chemistry. Transmuting single atoms generates molecules that have distinctly varied properties, thereby fostering potent molecular exchanges can be extensively used to synthesize functional molecules. Herein, we present a convenient protocol for nitrogen-carbon single-atom transmutations isoquinolines, which inspired by the Wittig reaction and enables easy access substituted naphthalene derivatives. The uses an inexpensive commercially available phosphonium ylide as carbon source furnish wide range of naphthalenes. key success this transformation formation triene intermediate through ring opening, undergoes 6π-electrocyclization elimination processes afford product. Furthermore, strategy facile synthesis 13 C-labeled naphthalenes using CH 3 PPh I commercial C facilitates modifying directing group C─H functionalization.

Language: Английский

---

Transition Metal-Catalyzed Nitrogen Atom Insertion into Carbocycles

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

Published: Feb. 26, 2025

ConspectusN-Heterocycles are essential in pharmaceutical engineering, materials science, and synthetic chemistry. Recently, skeletal editing, which involves making specific point changes to the core of a molecule through single-atom insertion, deletion, or transmutation, has gained attention for its potential modify complex substrates. In this context, insertion nitrogen atoms into carbocycles form N-heterocycles emerged as significant research focus modern chemistry owing novel logic. This distinctive retrosynthetic approach enables late-stage modification molecular skeletons provides different pathway synthesizing multiply substituted N-heterocycles. Nevertheless, atom proven challenging because inherent inertness carbon-based difficulty cleaving C-C bonds. Therefore, selective editing remains growing field Account primarily highlights contributions our laboratory active acknowledges key from other researchers. It is organized two sections based on type carbocycle. The first section explores cycloalkenes. Recent Co-catalyzed oxidative azidation strategies have enabled cyclobutenes, cyclopentenes, cyclohexenes, facilitating synthesis polysubstituted pyridines, been conventionally pyridine cross-coupling. subsequent discovery realm arenes. site-selective stable arenes We developed method intramolecular benzene rings 2-amino biaryls by suppressing competing C-H process using paddlewheel dirhodium catalyst. addition, address issues we employed arenols substrates, could act controlling elements editing. reported Cu-catalyzed arenols, proceeds dearomative azidation/aryl migration process, enabling incorporation Inspired result, recently extended reaction model Fe-catalyst facilitate ring contraction nitrogen-inserted product, achieving carbon-to-nitrogen transmutation arenols. Various polyaromatic effectively undergo desired atom's presenting considerable various applications Account, present an overview achievements reactions, with scopes, mechanistic features, applications. anticipate that will provide valuable insights propel development innovative methodologies both N-heterocycle synthesis.

Language: Английский

---

Skeletal Editing: Ring Insertion for Direct Access to Heterocycles

Molecules, Journal Year: 2024, Volume and Issue: 29(9), P. 1920 - 1920

Published: April 23, 2024

Skeleton editing has rapidly advanced as a synthetic methodology in recent years, significantly streamlining the synthesis process and gaining widespread acceptance drug development. This field encompasses diverse ring reactions, many of which exhibit immense potential skeleton editing, facilitating generation novel skeletons. Notably, reactions that involve cleavage two distinct rings followed by reformation new through insertion play pivotal role construction article aims to compile systematize this category emphasizing primary reaction types offering thorough exploration their associated complexities challenges. Our endeavor is furnish readers with comprehensive strategies, igniting research interest injecting fresh impetus into advancement domain.

Language: Английский

---

Skeletal Editing by Hypervalent Iodine Mediated Nitrogen Insertion

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 24, 2024

Hypervalent iodine reagents are versatile and readily accessible that have been extensively applied in contemporary synthesis modern organic chemistry. Among them, iodonitrene (ArI=NR), is a powerful reactive species, widely used for single-nitrogen-atom insertion reaction, skeletal editing to construct N-heterocycles. Skeletal with components has recently emerged as an exciting approach chemical transformation. These produce biologically relevant heterocycles functionalized molecular architectures. Recently, the of nitrogen-atom into hydrocarbons generate N-heterocyclic compounds using hypervalent significant focus field reactions. In this review, we discuss rapidly emerging nitrene insertion, including nitrogen access nitrogen-containing heterocycles, current mechanistic understanding these processes.

Language: Английский

---

Skeletal Editing Through Single Atom Insertion and Transmutation: An Insight into A New Era of Synthetic Organic Chemistry

Synthesis, Journal Year: 2024, Volume and Issue: 56(24), P. 3793 - 3814

Published: Aug. 20, 2024

Abstract Considering the importance of heterocycles, significantly represented in medicinal chemistry and drug development, single-atom insertion technique transmutation strategy provide productive approaches towards complicated molecular structures through heterocycle diversification. It shows a potentially powerful approach for modifying complex substrates concisely chemospecifically. Although skeletal editing applies to cyclic acyclic compounds, this review focuses on diversification carbo- heterocyclic compounds synthesizing various medicinally important molecules via technique. The classification system is based recent critical historical methods as applied aromatic rings. 1 Introduction 2 Skeletal Editing Carbon-Atom Insertion 2.1 Indoles Pyrroles Derivatives: into C=C Bond 2.2 Pyrazole Indazole an N–N 2.3 CF3 Group Heteroarenes 2.4 Imidazole C–N 2.5 Atom-to-Atom Transmutation 3 N-Atom 3.1 Nitrogen-Atom Carbocycles 3.2 Heterocycles 3.3 Carbon Nitrogen Molecular Isotopic 4 Conclusion

Language: Английский

---

Computational Access to 1,3,5,6,7‐Pentanitro‐3,6,7‐Triazabicyclo‐[3.1.1]‐Heptane (UIX): A Powerful Potential Explosive with Zero Oxygen Balance

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Abstract A novel cage nitramine, and potential explosive, 1,3,5,6,7‐pentanitro‐3,6,7‐triazabicyclo‐[3.1.1]‐heptane (UIX) with a zero‐oxygen balance was designed. It has high crystal density (ρ = 1.978 g/cm 3 ), outstanding propulsive detonation properties (Isp(s) neat 269.61; ρIsp(g cm −3 s) 533.29; P 42.55 GPa, D 9620 m/s), good sensitivity (h 50 9.06 cm) promising kinetic stability as CL‐20. Additionally, synthesis route for UIX is proposed.

Language: Английский

---

Diversification of Naphthol Skeletons Triggered by Aminative Dearomatization

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4910 - 4915

Published: May 31, 2024

A silver-catalyzed aminative dearomatization of naphthols has been developed and integrated into a stepwise approach for subsequent skeletal diversifications including ring expansion, opening, contraction, atom transmutation aryl scaffolds. This enables the synthesis diverse array azepinones, unsaturated amides, isoquinolines, indenones from naphthol substrates. Its application in bioactive functional molecules as well conversion complex molecular skeletons underscores its broad potential applicability. Mechanistic investigations suggest intermediacy dearomatized intermediates.

Language: Английский

---

Streamlining the Synthesis of Pyridones through Oxidative Amination of Cyclopentenones

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 27, 2024

Herein we report the development of an oxidative amination process for streamlined synthesis pyridones from cyclopentenones. Cyclopentenone building blocks can undergo in situ silyl enol ether formation, followed by introduction a nitrogen atom into carbon skeleton with successive aromatisation to yield pyridones. The reaction sequence is operationally simple, rapid, and carried out one pot. proceeds under mild conditions, exhibits broad functional group tolerance, complete regioselectivity, well scalable. developed method provides facile access

Language: Английский

---