C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine

Nature Synthesis, Год журнала: 2024, Номер 3(7), С. 913 - 921

Опубликована: Июнь 7, 2024

Язык: Английский

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

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 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.

Язык: Английский

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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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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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Direct Access to Quinazolines and Pyrimidines from Unprotected Indoles and Pyrroles through Nitrogen Atom Insertion

Organic Letters, Год журнала: 2023, Номер 25(47), С. 8419 - 8423

Опубликована: Ноя. 20, 2023

Recent advances in single-atom insertion reactions have opened up new synthetic approaches for molecular diversification. Developing innovative strategies to directly transform biologically relevant molecules, without any prefunctionalization, is key further expanding the scope and utility of such transformations. Herein, direct access quinazolines pyrimidines from corresponding unprotected 1H-indoles 1H-pyrroles reported, relying on implementation lithium bis(trimethylsilyl)amide (LiHMDS) as a novel nitrogen atom source combination with commercially available hypervalent iodine reagents. Further application this strategy late-stage settings demonstrates its potential lead structure diversification campaigns.

Язык: Английский

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Toward the Generation of 2-Amino-3-Formyl Difunctionalized Chromones via Pd-Enabled Rearrangement Strategy

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 12692 - 12699

Опубликована: Сен. 14, 2023

Accomplished herein is a rearrangement strategy for the highly efficient assembly of synthetically cumbersome while medicinally significant 2-amino-3-formyl chromones via palladium-catalyzed ring-opening, rearrangement, and cyclization process. Such sequence enables formation one C(sp2)–O bond C(sp2)–C(sp2) bond, reconstruction benzo-γ-pyrone moiety in single operation, thus producing difunctionalized chromone-incorporated derivatives. The reaction proceeds shorter time (30 min 3-iodochromones most cases) atom- step-economical manner. synthetic application current protocol further demonstrated by late-stage modification pharmaceuticals their intermediates, gram-scale reactions, transformations functional groups, as well synthesis bioactive molecules drugs. Mechanistic studies indicate that nucleophilic ring-opening process moiety, phenoxy anion intermediate, an intramolecular might be involved present system.

Язык: Английский

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Skeletal Editing of Cyclic Molecules Using Nitrenes

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(21), С. 2656 - 2667

Опубликована: Июль 16, 2024

Comprehensive Summary Nitrenes, as neutral monovalent nitrogen‐centered molecular species, can insert into various bond or remove nitrogen atoms from amines. Nitrene assisted single‐atom skeletal editing, discovered decades ago, provides an efficient approach for the precise alteration of cyclic skeletons. In this review, we briefly summarize early studies on editing frameworks involving nitrene and introduce several recent important advances systematically.

Язык: Английский

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Selective nitrogen insertion into aryl alkanes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 17, 2024

Abstract Molecular structure-editing through nitrogen insertion offers more efficient and ingenious pathways for the synthesis of nitrogen-containing compounds, which could benefit development synthetic chemistry, pharmaceutical research, materials science. Substituted amines, especially alkyl heterocyclic are widely found in nature products drugs. Generally, accessing these compounds requires multiple steps, result low efficiency. In this work, a molecular editing strategy is used to realize using aryl alkanes as starting materials. Using derivatives O -tosylhydroxylamine source, method enables precise into C sp 2 -C 3 bond alkanes. Notably, further applications demonstrate that be prepare bioactive molecules with good efficiency modify skeleton Furthermore, plausible reaction mechanism involving transformation carbocation imine intermediates has been proposed based on results control experiments.

Язык: Английский

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Rh-Catalyzed Enantioselective Single-Carbon Insertion of Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21837 - 21846

Опубликована: Июль 26, 2024

The interest in the discovery and development of skeletal editing processes that selectively insert, exchange, or delete an atom organic molecules has significantly increased over last few years. However, this class proceed through creation a chiral center with high asymmetric induction have been largely unexplored. Herein, we report enantioselective single-carbon insertion aryl- alkyl-substituted alkenes mediated by catalytically generated Rh-carbynoid phosphate nucleophiles produce enantioenriched allylic phosphates (enantiomeric ratio (e.r.) = 89.5:10.5-99.5:0.5). key to process was diastereo- cyclopropanation alkene formation transient cyclopropyl-I

Язык: Английский

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One‐Carbon Ring Expansion of Indoles and Pyrroles: A Straightforward Access to 3‐Fluorinated Quinolines and Pyridines

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 12, 2023

Abstract 3‐Fluorinated quinolines and pyridines are prevalent pharmacophores, yet their synthesis is often challenging. Herein, we demonstrate that dibromofluoromethane as bromofluorocarbene source enables the one‐carbon ring expansion of readily available indoles pyrroles to structurally diverse 3‐fluorinated pyridines. This straightforward protocol requires only a short reaction time ten minutes can be performed under air atmosphere. Preliminary investigations reveal this strategy also applied other valuable azines by using different 1,1‐dibromoalkanes bromocarbene sources.

Язык: Английский

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