Bifunctional sulfilimines enable synthesis of multiple N-heterocycles from alkenes

Nature Chemistry, Год журнала: 2022, Номер 14(8), С. 898 - 904

Опубликована: Июль 25, 2022

Abstract Intramolecular cyclization of nitrogen-containing molecules onto pendant alkenes is an efficient strategy for the construction N-heterocycles, which are paramount importance in, example, pharmaceuticals and materials. Similar intermolecular reactions, however, scarcer nitrogen building blocks, including N-centred radicals, divergent modular versions not established. Here we report use sulfilimines as bifunctional N-radical precursors reactions with to produce N-unprotected heterocycles in a single step through photoredox catalysis. Structurally diverse can be synthesized step, subsequently engage afford synthetically valuable five-, six- seven-membered heterocycles. The broad scope achievable by radical-polar crossover annulation enabled character reagents, distinguishes itself from all other N-centred-radical-based reactions. synthesis allows larger structural diversity N-heterocycle products than currently methods.

Язык: Английский

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Regiodivergent Electrophotocatalytic Aminooxygenation of Aryl Olefins

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(41), С. 18803 - 18809

Опубликована: Окт. 4, 2022

A method for the regiodivergent aminooxygenation of aryl olefins under electrophotocatalytic conditions is described. The procedure employs a trisaminocyclopropenium (TAC) ion catalyst with visible light irradiation controlled electrochemical potential to convert corresponding oxazolines high chemo- and diastereoselectivity. With judicious choice between two inexpensive abundant reagents, namely water urethane, either 2-amino-1-ol or 1-amino-2-ol derivatives could be prepared from same substrate. This amenable multigram synthesis oxazoline products low loadings.

Язык: Английский

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Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8299 - 8307

Опубликована: Апрель 6, 2023

Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents opportunity deliver two unique nucleophiles across alkene. Unfortunately, the selectivity profiles known dielectrophiles largely precluded this deceptively simple synthetic approach. Herein, we demonstrate that dicationic adducts generated through electrolysis alkenes and thianthrene possess profile relative more conventional dielectrophiles. Specifically, these species undergo single perfectly regioselective substitution reaction with phthalimide salts. This observation unlocks appealing new platform for aminofunctionalization reactions. As illustrative example, implement reactivity paradigm address longstanding challenge: diamination distinct nitrogen nucleophiles. Studies mechanism process reveal key alkenyl thianthrenium salt intermediate controls exquisite regioselectivity highlight importance proton sources in controlling sulfonium electrophiles.

Язык: Английский

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Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles

ACS Catalysis, Год журнала: 2023, Номер 13(20), С. 13301 - 13309

Опубликована: Окт. 2, 2023

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords broad range compounds that bear phenolic hydroxyl group as useful synthetic handle and, thus, enriches the toolbox for rapid generation molecular complexity. control experiments and DFT calculations indicate dual-hydrogen-bonding bridge formed between substrate TfO– anion plays crucial role in determining enantioselectivity transformation.

Язык: Английский

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Mechanochemical synthesis of organoselenium compounds

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

Опубликована: Янв. 26, 2024

We disclose herein a strategy for the rapid synthesis of versatile organoselenium compounds under mild conditions. In this work, magnesium-based selenium nucleophiles are formed in situ from easily available organic halides, magnesium metal, and elemental via mechanical stimulation. This process occurs liquid-assisted grinding (LAG) conditions, requires no complicated pre-activation procedures, operates broadly across diverse range aryl, heteroaryl, alkyl substrates. symmetrical diselenides efficiently obtained after work-up air, while one-pot nucleophilic addition reactions with various electrophiles allow comprehensive unsymmetrical monoselenides high functional group tolerance. Notably, method is applied to regioselective selenylation diiodoarenes polyaromatic aryl halides that difficult operate solution approaches. Besides selenium, sulfur tellurium also competent process, which showcases potential methodology facile organochalcogen compounds.

Язык: Английский

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Catalytic Enantioselective Aminative Difunctionalization of Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 7029 - 7038

Опубликована: Март 1, 2024

Enantioselective difunctionalization of alkenes offers a straightforward means for the rapid construction enantioenriched complex molecules. Despite tremendous efforts devoted to this field, enantioselective aminative remains challenge, particularly through an electrophilic addition fashion. Herein, we report unprecedented approach via copper-catalyzed with external azo compounds as nitrogen sources. A series valuable cyclic hydrazine derivatives either [3 + 2] cycloaddition or intramolecular cyclization have been achieved in high chemo-, regio-, enantio-, and diastereoselectivities. In transformation, wide range functional groups, such carboxylic acid, hydroxy, amide, sulfonamide, aryl could serve nucleophiles. Importantly, new cyano oxazoline chiral ligand was found play crucial role control enantioselectivity.

Язык: Английский

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Asymmetric Synthesis with Organoselenium Compounds – The Past Twelve Years

Chemistry - A European Journal, Год журнала: 2024, Номер 30(21)

Опубликована: Янв. 11, 2024

Abstract The discovery and synthetic applications of novel organoselenium compounds their reactions proceeded rapidly during the past fifty years such processes are now carried out routinely in many laboratories. At same time, growing demand for new enantioselective provided challenges. convergence selenium chemistry asymmetric synthesis led to key developments 1970s, although majority early work was based on stoichiometric processes. More recently, greater emphasis has been placed greener catalytic variations, along with a deeper understanding mechanisms. present review covers literature this field from 2010 2023 encompasses mediated by chiral selenium‐based reagents, auxiliaries, especially, catalysts. Protocols achiral conjunction other species catalysts, as well that controlled substrates, also included.

Язык: Английский

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Recent progress in the organoselenium-catalyzed difunctionalization of alkenes

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Язык: Английский

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Electrochemical Organoselenium-Catalyzed Intermolecular Hydroazolylation of Alkenes with Low Catalyst Loadings

Organic Letters, Год журнала: 2022, Номер 24(29), С. 5345 - 5350

Опубликована: Июль 19, 2022

The organoselenium-catalyzed amination of alkenes is a promising way to construct functionalized amines. However, the use chemical oxidants and unavoidable formation allylic amine or enamine are two main limitations these methodologies. Against this background, we herein report an electro-selenocatalytic regime for hydroazolylation with azoles under external oxidant-free conditions low catalyst loadings. Moreover, protocol enables generation amines without vinyl substituents.

Язык: Английский

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Selenylation Chemistry Suitable for On‐Plate Parallel and On‐DNA Library Synthesis Enabling High‐Throughput Medicinal Chemistry

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(35)

Опубликована: Май 17, 2022

Abstract Click chemistry is a concept wherein modular synthesis used for rapid functional discovery. To this end, continuous discovery of clickable chemical transformations the pillar to support development field. This report details C3‐H selenylation indole that suitable on‐plate parallel and DNA‐encoded library ( Se DEL) via bioinspired LUMO activation strategy. reaction modular, robust highly site‐selective, it features simple mild system (catalyzed by nonmetallic B(C 6 F 5 ) 3 at room temperature), high yields excellent group compatibility. Using method, 1350 indole‐selenides was synthesized in an efficient practical manner, enabling identification ai as promising compound with nanomolar antiproliferative activity cancer cells situ phenotypic screening. These results indicate great potential new high‐throughput medicinal biology.

Язык: Английский

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