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

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4041 - 4053

Опубликована: Янв. 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.

Язык: Английский

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Skeletal Editing by Hypervalent Iodine Mediated Nitrogen Insertion

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 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.

Язык: Английский

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

Science Advances, Год журнала: 2025, Номер 11(5)

Опубликована: Янв. 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.

Язык: Английский

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Controllable Molecular Editing of 2-Amino-N-substituted Benzamides: Site-selective Synthesis of 6-Selenylated N-Substituted 1,2,3-Benzotriazine-4(3H)-ones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

We present an efficient silver-catalyzed one-pot controllable molecular editing protocol for the transformation of 2-amino-N-substituted benzamides into 6-selenylated N-substituted 1,2,3-benzotriazine-4(3H)-ones under mild reaction conditions. This three-component strategy is achieved by building N-N/N═N/C-Se bonds, which provides a practical pathway preparation selenylated with broad substrate scope and good functional group tolerance, as well high site-selectivity. Mechanistic experiments suggest that this proceeds via intermolecular site-selective C-H selenylation readily available diselenides, followed annulation using AgNO3 nitrogen synthon.

Язык: Английский

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Transition Metal-Catalyzed Nitrogen Atom Insertion into Carbocycles

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

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Atom-swapping skeletal editing of benzo[c]oxepines for the construction of 2-benzodiazepines via a continuous manufacturing one-pot synthesis

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111200 - 111200

Опубликована: Апрель 1, 2025

Язык: Английский

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Fluorescent pyridine phosphonium salts via transmutation of metallabenzenes

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 16, 2025

Metallabenzenes are recognized as a unique class of aromatic compounds, not only structural and theoretical interest but also platforms to design powerful transformations. Here, we report the successful transmutation metallabenzene for pyridine synthesis. This 'metal-to-nitrogen swapping' process utilizes readily available ruthenabenzene phosphonium salts commercially 2-aminopyridines under mild conditions. The isolation ruthena-azepines, containing planar seven-membered aza-metallacycle, along with DFT calculations, supports nitrogen insertion/metal deletion cascade driven by aromatization. Additionally, investigate tunable photophysical properties resulting salts.

Язык: Английский

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Skeletal Editing via Transition‐Metal‐Catalyzed Nitrene Insertion

The Chemical Record, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 28, 2024

Abstract Metal‐nitrenes are valuable reactive intermediates for synthesis and widely used to construct biologically relevant scaffolds, complexes functionalized molecules. The ring expansion of cyclic molecules via single‐nitrogen‐atom insertion nitrene or metal‐nitrenoid has emerged as a promising modern strategy driving advantageous nitrogen‐rich compound synthesis. In recent years, the catalytic single nitrogen atom into carbocycles, leading N‐heterocycles, become an important focus synthetic approaches with applications in medicinal chemistry, materials science, industry. Catalytic insertions have been increasing prominence organic due their capability high‐value added nitrogen‐containing heterocycles from simple feedstocks. this review, we will discuss rapidly growing field skeletal editing using transition metal catalysis access heterocycles, on across wide spectrum carbocycles.

Язык: Английский

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