Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines

Science Advances, Год журнала: 2025, Номер 11(3)

Опубликована: Янв. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Язык: Английский

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Electron-Donor-Mediated Divergent Transformation of Br–R_F via EDA Complex for the Synthesis of Fluorine-Containing Oxindoles and Amides

Organic Letters, Год журнала: 2024, Номер 26(46), С. 9990 - 9995

Опубликована: Ноя. 11, 2024

We have developed an unprecedented electron-donor-controlled divergent reaction between

Язык: Английский

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Synthesis of (–)-Sedacryptine and (–)-Geissman-Waiss Lactone by Applying Methods for the Direct Transformation of Amides

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(3), С. 988 - 988

Опубликована: Янв. 1, 2025

Язык: Английский

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Deoxygenative Alkynylation of Amides via C=O Bond Cleavage

Chemical Communications, Год журнала: 2024, Номер 60(64), С. 8454 - 8457

Опубликована: Янв. 1, 2024

A novel deoxygenative alkynylation of amides promoted by a synergistic action divalent rare-earth element and transition metal has been developed. In this method, α-alkynyl substituted amines are synthesized from unactivated alkynes in single transformation. Broad substrate scope excellent selectivity for CO cleavage demonstrated. This approach represents general method the construction versatile amide bonds.

Язык: Английский

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Substituent-Controlled Copper-Catalyzed Trifluoromethylation of 1,7-Dienes: Synthesis of Mono- and Bis-trifluoromethylated Benzoxepines

Organic Letters, Год журнала: 2024, Номер 26(34), С. 7261 - 7266

Опубликована: Авг. 21, 2024

A copper-catalyzed trifluoromethylation of benzene-linked 1,7-dienes with 1-trifluoromethyl-1,2-benziodoxole via a radical cascade cyclization process for the synthesis mono- and bis-trifluoromethylated benzoxepines is developed. The selectivity depends on substituents double bond allyl group in 1,7-dienes. large-scale operation late-stage functionalization bioactive molecules reveal promising utility this protocol.

Язык: Английский

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Recent Advances on Fluorine Chemistry

International Journal of Molecular Sciences, Год журнала: 2024, Номер 25(15), С. 8251 - 8251

Опубликована: Июль 28, 2024

The purpose of this Special Issue is to showcase the latest findings in fluorine chemistry [...]

Язык: Английский

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Samarium Diiodide/Samarium-Mediated Direct Deoxygenative Hydroborylation of Ketones with Hydroborane Esters

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

A direct deoxygenative hydroborylation of ketones with hydroborane ester promoted by a combination samarium diiodide, and nickel has been developed.

Язык: Английский

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Organocatalytic Deoxygenative [3+2] Cycloaddition of N-Hydroxyamides with Alkynes to Access Isoxazoles

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Although the transition-metal-catalyzed [3+2] cycloadditions to access isoxazoles have been described well, organocatalytic methods remain underdeveloped. Herein, we report use of an organophosphine catalyst for preparation a series with exceptional regioselectivity via cycloaddition

Язык: Английский

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Deoxygenative Geminal Silylboration of Amides Using Silylboronates: Synthesis and Use of α‐Boryl‐α‐Silylalkylamines

Angewandte Chemie, Год журнала: 2024, Номер 136(45)

Опубликована: Авг. 6, 2024

Abstract α‐Silylalkylamines and α‐borylalkylamines are versatile synthetic intermediates attractive scaffolds found in pharmaceutical drugs agrochemicals. Despite great progress on methods for preparation of α‐silylalkylamines or α‐borylalkylamines, there no general strategies α‐boryl‐α‐silylalkylamines the reactivity has not been explored. Here we report deoxygenative geminal silylboration amides using silylboronates presence alkoxide base catalyst, producing α‐boryl‐α‐silylalkylamines. The silicon boron groups to be utilized chemoselective transformations, such as protonation alkylation. This protocol serves various from readily available amides.

Язык: Английский

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Deoxygenative Geminal Silylboration of Amides Using Silylboronates: Synthesis and Use of α‐Boryl‐α‐Silylalkylamines

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Авг. 6, 2024

Abstract α‐Silylalkylamines and α‐borylalkylamines are versatile synthetic intermediates attractive scaffolds found in pharmaceutical drugs agrochemicals. Despite great progress on methods for preparation of α‐silylalkylamines or α‐borylalkylamines, there no general strategies α‐boryl‐α‐silylalkylamines the reactivity has not been explored. Here we report deoxygenative geminal silylboration amides using silylboronates presence alkoxide base catalyst, producing α‐boryl‐α‐silylalkylamines. The silicon boron groups to be utilized chemoselective transformations, such as protonation alkylation. This protocol serves various from readily available amides.

Язык: Английский

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