Multicomponent Synthesis of α-Branched Amines via a Zinc-Mediated Carbonyl Alkylative Amination Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9045 - 9062

Опубликована: Март 15, 2024

Methods for the synthesis of α-branched alkylamines are important due to their ubiquity in biologically active molecules. Despite development many methods amine preparation, C(sp3)-rich nitrogen-containing compounds continue pose challenges synthesis. While carbonyl reductive amination (CRA) between ketones and is cornerstone method alkylamine synthesis, it sometimes limited by sterically demanding condensation step dialkyl amines more restricted availability compared aldehydes. We recently reported a "higher-order" variant this transformation, alkylative (CAA), which utilized halogen atom transfer (XAT)-mediated radical mechanism, enabling streamlined complex alkylamines. efficacy visible-light-driven approach, displayed scalability issues, competitive was problem certain substrate classes, limiting applicability. Here, we report change reaction regime that expands CAA platform through realization an extremely broad zinc-mediated reaction. This new strategy enabled elimination CRA, simplified purification, improved scope. Furthermore, harnessed carboxylic acid derivatives as alkyl donors facilitated α-trialkyl tertiary amines, cannot be accessed via CRA. Zn-mediated can carried out at variety scales, from 10 μmol setup microtiter plates high-throughput experimentation, gram-scale medicinally-relevant compounds. believe transformation enables robust, efficient, economical access provides viable alternative current benchmark methods.

Язык: Английский

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Photocatalytic Decarboxylative Alkylation of Cyclic Imine–BF₃ Complexes: A Modular Route to Functionalized Azacycles

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Alkyl radicals generated via an acridine photocatalyzed decarboxylation reaction of feedstock carboxylic acids engage with a range cyclic imine-BF

Язык: Английский

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Radical Substitution of Polyfluoroarenes and Heteroarenes Promoted by Photoredox Activation of Organozinc Iodides

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(19), С. 3387 - 3391

Опубликована: Сен. 12, 2023

Abstract Aromatic compounds interact with organozinc reagents under photoredox conditions, leading to the substitution products. The reaction is performed blue light irradiation via in situ generated (Barbier conditions), which are oxidized by photocatalyst, followed radical attack at aromatic substrate. method works polyfluorinated arenes, 2‐chlorobenzoxazoles, and 2‐sulfonyl‐substituted benzothiazole.

Язык: Английский

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One-Pot Transformation of Aldehydes to Ketones via Minisci-Type Reaction of Imines

Organic Letters, Год журнала: 2023, Номер 25(48), С. 8751 - 8755

Опубликована: Ноя. 28, 2023

A method for the conversion of aldehydes to ketones via preliminary formation aldiminines is described. The imines are involved in acid promoted Minisci-type reaction with alkyl radicals generated from esters N-hydroxylphthalimide under photoredox conditions. Aminyl radical cations formed after addition iminium ions believed be key intermediates, which determine outcome.

Язык: Английский

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One-Pot Domino Catalysis to Construct Alkyl/Aryl Pyrroles Initiated by Pd-TMM Annulation of Unactivated Imines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

Herein, a one-pot domino catalyzed three-component process is described, which initiated by palladium/zinc cooperatively cycloaddition between trimethylenemethane (TMM) and unactivated alkyl/aryl imines, followed isomerization Zn(OTf)2-catalyzed DDQ oxidation, furnishing valuable substituted pyrroles. We disclose that the cooperative catalysis affords dual-Zn(OTf)2-stabilized azapalladacycle, wherein Pd–N bond polarized Zn(OTf)2, facilitating unique outer-sphere allylic amination. Moreover, subsequent dehydrogenation can be feasibly promoted zinc catalysis.

Язык: Английский

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Unlocking the Reactivity of the C-In Bond: Alkyl Indium Reagents as a Source of Radicals Under Photocatalytic Conditions

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Generation of organic radicals from organometallic compounds is a key step in metallaphotoredox cross-coupling reactions. The ability organoindium to serve as sources alkyl under light promoted oxidative conditions described. Organoindium reagents were used dual photocatalytic/nickel with aryl bromides. These can be conveniently obtained primary, secondary and tertiary bromides chlorides using novel indium(i) bromide/lithium bromide system. Both steps, the formation organoindiums their are insensitive towards air moisture tolerate wide variety functional groups.

Язык: Английский

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Controlled synthesis of polymers in the light of green chemistry

Russian Chemical Reviews, Год журнала: 2025, Номер 94(4), С. RCR5164 - RCR5164

Опубликована: Апрель 1, 2025

The discovery of reversible deactivation radical polymerization (RDRP), or controlled (CRP) has revolutionized the chemistry synthetic polymers. This strategy opened up way to polymer materials with architecture, composition, and functions. Currently, owing use novel approaches related chain deactivation, gone beyond synthesis. It can be used obtain not only macromolecular organic compounds, but also organic-inorganic hybrid materials, bioconjugates, promising polymers for electronics, energy production, medicine, other high-tech fields. is exceptionally important that some CRP methods have a clear-cut environmental component, since they are focused on compliance most principles green development nature-like processes in targeted synthesis well-defined specified set properties characteristics. review considers particular examples analyzes possible prospects practical application environmentally benign functional A comparative analysis performed classical living wide range monomers (reversible inhibition, addition fragmentation transfer, atom transfer involving transition metal complexes), concept photoredox catalysis, methodology as applied gives above aspects, including procedural details photoinitiation their relationship key principles. In our opinion, this will interest specialists field chemistry, chemists scientists. <br> bibliography includes 242 references.

Язык: Английский

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Zinc Chelate Complexes of N‐Acyl Hydrazones as Substrates for Addition of Alkyl and Fluorinated Radicals

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(15), С. 2636 - 2642

Опубликована: Июль 13, 2023

Abstract Zinc chelate complexes can be generated in situ from N‐acyl hydrazones by treatment with isopropyl zinc iodide. These couple alkyl and fluorinated radicals under photoredox conditions. Alkyl were organozinc halides using an organic photocatalyst afford hydrazines as a result of reductive mode addition. Fluorinated formed perfluorinated iodides conditions leading to fluoroalkylated via neutral reaction pathway.

Язык: Английский

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BF₂‐Chelates of N‐Acylhydrazones as Versatile Coupling Partners in Photoredox Promoted Reactions

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(22)

Опубликована: Май 3, 2023

Abstract Five‐membered difluoroboryl chelate complexes are competent substrates for radical reactions with various precursors including potassium trifluoroborates, bis(catecholato)siliconates, 4‐alkyl‐substituted Hantzsch esters, dihydroquinazolinones, esters of N ‐hydroxyphthalimide, Katritzky salts, alkyl iodides and thiols. Using these reagents, primary, secondary, tertiary radicals can be generated under oxidative or reductive conditions add at the C=N bond chelates leading to hydrazide products.

Язык: Английский

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Photoinduced radical alkylation of aldehydes with potassium alkyltrifluoroborates

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 3988 - 3996

Опубликована: Янв. 1, 2024

A method for radical addition at aldehydes is described. The reaction based on the interplay of attack and cleavage processes occurring a boron complexed carbonyl group.

Язык: Английский

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