Cobalt-catalyzed synthesis of amides from alkenes and amines promoted by light

Science, Год журнала: 2024, Номер 383(6678), С. 77 - 81

Опубликована: Янв. 4, 2024

Catalytic methods to couple alkene and amine feedstocks are valuable in synthetic chemistry. The direct carbonylative coupling of alkenes amines holds promise as a perfectly atom-economical approach amide synthesis, but general remain underdeveloped. Herein, we report an hydroaminocarbonylation catalyzed by unmodified, inexpensive cobalt carbonyl under mild conditions low pressure promoted light. Silane addition after the reaction enables sequential cobalt-catalyzed reduction, constituting formal hydroaminomethylation. These exhibit exceptional scope across both components with high chemo- regioselectivity proceed efficiently even absence solvent. formation hydridocobalt through photodissociation ligand is proposed enable catalytic activity conditions, which addresses long-standing challenge catalysis.

Язык: Английский

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Aminoalkylation of Alkenes Enabled by Triple Radical Sorting

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.

Язык: Английский

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Recent advances in C(sp³)–N bond formation via metallaphoto-redox catalysis

Chemical Communications, Год журнала: 2024, Номер 60(50), С. 6340 - 6361

Опубликована: Янв. 1, 2024

In this review, the state-of-the-art advances in radical-involved C(sp 3 )–N bond formation via metallaphotoredox catalysis have been highlighted, which are organized according to different catalytic modes, reaction types, and substrate classes.

Язык: Английский

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Emergence of a distinct mechanism of C–N bond formation in photoenzymes

Nature, Год журнала: 2024, Номер unknown

Опубликована: Окт. 8, 2024

Язык: Английский

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Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(40), С. 21738 - 21744

Опубликована: Окт. 3, 2023

We report a light-driven method for the intermolecular anti-Markovnikov hydroamination of alkenes with primary heteroaryl amines. In this protocol, electron transfer between an amine substrate and excited-state iridium photocatalyst affords aminium radical cation (ARC) intermediate that undergoes C–N bond formation nucleophilic alkene. Integral to reaction success is electronic character amine, wherein increasingly electron-deficient amines generate reactive ARCs. Counteranion-dependent reactivity observed, triflate photocatalysts are employed in place conventional hexafluorophosphate complexes. This exhibits broad functional group tolerance across 55 examples N-alkylated products derived from pharmaceutically relevant

Язык: Английский

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Concise synthesis of pyrrolo[3,4-c]quinolines via a P(NMe₂)₃-catalyzed [4 + 2] annulation followed by a Zn/AcOH-mediated reduction–hydroamination–isomerization

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(10), С. 2762 - 2767

Опубликована: Янв. 1, 2024

A P(NMe2)3-catalyzed [4 + 2] annulation of 2-amino-β-nitrostyrenes and β′-acetoxy allenoates followed by a Zn/AcOH-mediated reduction–hydroamination–isomerization has been developed.

Язык: Английский

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Organic Synthesis Away from Equilibrium: Contrathermodynamic Transformations Enabled by Excited-State Electron Transfer

Accounts of Chemical Research, Год журнала: 2024, Номер 57(13), С. 1827 - 1838

Опубликована: Июнь 21, 2024

ConspectusChemists have long been inspired by biological photosynthesis, wherein a series of excited-state electron transfer (ET) events facilitate the conversion low energy starting materials such as H

Язык: Английский

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MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10² h^–1 Turnover Frequencies

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 20, 2025

Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis active materials in supercapacitors. In comparison, there are only a few reports on as thermal catalysts for general organic reactions. Herein, unprecedented catalytic activity Ti3C2 MXene hydroamination alkynes is reported, overcoming limitations poor activity, lack selectivity, stability, which generally encountered solid known so far. case Ti3C2, exhibits almost complete selectivity anti-Markovnikov regioisomer, both aliphatic amines less-reactive aromatic amines. also efficiently catalyzes intramolecular hydroamination, leading formation indol heterocycles. The C-C multiple bonds reaction with atom efficiency that may form C-N from convenient reagents. maximum number sites nanosheets quantified by thermoprogrammed NH3 desorption. measured TOF values order 102 h-1, highest value being 350 h-1 1-hexyne n-butylamine. Therefore, among heterogeneous studied, its per site comparable best reported Density functional theory calculations models indicate cooperation neighboring Ti atoms mechanism. Considering compositional structural versatility MXenes, present findings open door further application other

Язык: Английский

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Iridium‐Catalyzed Remote Site‐Switchable Hydroarylation of Alkenes Controlled by Ligands

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(41)

Опубликована: Авг. 23, 2023

An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering the products functionalized at subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields with to excellent site-selectivities. The catalytic system showed functional group tolerance a broad substrate scope, including unactivated activated alkenes. More importantly, regioconvergent transformations mixtures isomeric were also successfully realized. results mechanistic studies demonstrate that reaction undergoes chain-walking process give [Ar-Ir-H] complex alkene. subsequent processes proceed through modified Chalk-Harrod-type mechanism via migratory insertion alkene into Ir-C bond followed C-H reductive elimination afford hydrofunctionalization site-selectively.

Язык: Английский

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Ligand-Exchange-Enabled Axially Chiral Recognition in Asymmetric Aminopalladation/Olefination of 2-Alkynylanilides

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4053 - 4065

Опубликована: Март 1, 2024

Chiral recognition for the synthesis of axially chiral biaryl units is a fundamental and challenging topic in organic synthesis. Herein, we documented that an efficient O-ligand exchange between catalyst substrate enabled axial asymmetric aminopalladation/olefination 2-alkynylanilides vinyl trifluoromethanesulfonates, providing 3-alkenylindoles with up to 97% ee 98% yield. This protocol features mild conditions, broad functional group tolerance, scalability, late-stage modification bioactive molecules. Experimental computational studies hinted (R)-BIDIME/Pd complex alkoxy was crucial success stereoselectivity control.

Язык: Английский

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