Defluorinative functionalization approach led by difluoromethyl anion chemistry

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 7, 2025

Язык: Английский

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Catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides via selective C-F bond activation

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Июнь 18, 2021

Abstract A regioselective carbosilylation of alkenes has emerged as a powerful strategy to access molecules with functionalized silylated alkanes, by incorporating silyl and carbon groups across an alkene double bond. However, the best our knowledge, organic fluorides have never been used in this protocol. Here we disclose catalyst-free using boronates mediated t BuOK. The main feature transformation is selective activation C-F bond fluoride boronate without undergoing potential side-reactions involving C-O, C-Cl, heteroaryl-CH, even CF 3 groups. Various alkanes tertiary or quaternary centers that aromatic, hetero-aromatic, and/or aliphatic at β -position are synthesized single step from substituted non-substituted aryl alkenes. An intramolecular variant also achieved via reaction fluoroarene ω-alkenyl side chain boronate.

Язык: Английский

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Insertion of Diazo Esters into C–F Bonds toward Diastereoselective One-Carbon Elongation of Benzylic Fluorides: Unprecedented BF₃ Catalysis with C–F Bond Cleavage and Re-formation

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(49), С. 20616 - 20621

Опубликована: Ноя. 12, 2021

Selective transformation of C–F bonds remains a significant goal in organic chemistry, but insertion one-carbon-atom unit has never been established. Herein we report the BF3-catalyzed formal diazo esters as sources into to accomplish one-carbon elongation benzylic fluorides. A DFT calculation study revealed that BF3 catalyst could contribute both bond cleavage and re-formation. This provided α-fluoro-α,β-diaryl with high level diastereoselectivity. Various fluorides were applicable. The synthetic utility this method was demonstrated by synthesis fluoro analogue compound is used transient receptor potential canonical channel inhibitor.

Язык: Английский

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A Carbene Strategy for Progressive (Deutero)Hydrodefluorination of Fluoroalkyl Ketones

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(7)

Опубликована: Дек. 10, 2021

Hydrodefluorination is one of the most promising chemical strategies to degrade perfluorochemicals into partially fluorinated compounds. However, controlled progressive hydrodefluorination remains a significant challenge, owing decrease in strength C-F bonds along with defluorination. Here we describe carbene strategy for sequential (deutero)hydrodefluorination perfluoroalkyl ketones under rhodium catalysis, allowing controllable preparation difluoroalkyl- and monofluoroalkyl from aryl- even alkyl-substituted perfluoro-alkyl high yield excellent functional group tolerance. The reaction mechanism origin intriguing chemoselectivity were rationalized by density theory (DFT) calculations.

Язык: Английский

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Difluorocarbene enables to access 2-fluoroindoles from ortho-vinylanilines

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Авг. 17, 2021

2-Fluoroindoles as an important structural scaffold are widely existing in many bioactive or therapeutic agents. Despite their potential usefulness, efficient constructions of 2-fluoroindole derivatives very sparce. The development straightforward synthetic approaches to access 2-fluoroindoles is highly desirable for studying fundamental properties and applications. Herein, we report general strategy the construction which a wide variety were accessed with high efficiency chemoselectivity. Instead starting from indole skeletons, our constructs scaffolds alongside incorporation fluorine atom on C2 position formal [4+1] cyclization readily accessible ortho-vinylanilines difluorocarbene. In protocol, commercially halodifluoroalkylative reagents provide one carbon by cleaving C-N tertiary bond forming C-C double ortho-vinylanilines. Downstream transformations lead various valuable molecules demonstrated significant advantages over previous reports. And mechanistic studies suggest that reaction undergoes cascade difluorocarbene-trapping intramolecular Michael addition followed Csp3-F cleavage.

Язык: Английский

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Carbodefluorination of fluoroalkyl ketones via a carbene-initiated rearrangement strategy

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Июль 25, 2022

The C-F bond cleavage and C-C formation (i.e., carbodefluorination) of readily accessible (per)fluoroalkyl groups constitutes an atom-economical efficient route to partially fluorinated compounds. However, the selective mono-carbodefluorination trifluoromethyl (CF

Язык: Английский

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Nickel-Catalyzed Exhaustive Hydrodefluorination of Perfluoroalkyl Arenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 11449 - 11456

Опубликована: Май 4, 2023

Perfluoroalkyl compounds are persistent environmental pollutants due to their strong C(sp3)-F bonds. Hydrodefluorination has emerged as a potential alternative disposal method for perfluoroalkyl compounds. Although the transformation of trifluoromethyl arenes into corresponding methyl been studied by several research groups, hydrodefluorination reactions longer chains remain rare. Herein, we report exhaustive pentafluoroethyl and longer-chain analogues using molecular nickel catalysis. Despite cleavage multiple bonds, reaction already proceeds upon gentle heating (60 °C). A mechanistic investigation indicated that via benzylic followed homobenzylic ones. We reveal roles Ni catalyst, which include C-F bond cleavage, promotion HF elimination, hydrosilylation.

Язык: Английский

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α‐Difluoroalkylation of Benzyl Amines with Trifluoromethylarenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 19, 2023

Abstract An α‐difluoroalkylation of benzyl amines with trifluoromethylarenes is disclosed herein. This protocol characterized by its operational simplicity, excellent chemoselectivity and broad scope—even advanced synthetic intermediates—, thus offering a new entry point to medicinally‐relevant α‐difluoroalkylated from simple, yet readily accessible, precursors.

Язык: Английский

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Development and Mechanistic Studies of (E)-Selective Isomerization/Tandem Hydroarylation Reactions of Alkenes with a Nickel(0)/Phosphine Catalyst

ACS Catalysis, Год журнала: 2021, Номер 11(11), С. 6741 - 6749

Опубликована: Май 26, 2021

A stereoselective alkene isomerization and sequential hydroarylation with arylboronic acid using a nickel(0) catalyst has been developed. The bulky monophosphine PAd2(n-Bu) is an effective ligand in these reactions to furnish both various stereo-defined internal alkenes products (isomerization: up 98%, E/Z = 98:2; tandem hydroarylation: 82%). Mechanistic studies based on experiments computational calculations suggested that the proceeds via intra- or intermolecular hydrogen shift. Furthermore, concerted multibond recombination boronic acid-assisted oxidative protometallation of was found be reasonable mechanism for formation alkylnickel(II) species from alkene, nickel(0), alcohol, hydroarylation.

Язык: Английский

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Photochemical and Electrochemical Strategies for Hydrodefluorination of Fluorinated Organic Compounds

Chemistry - A European Journal, Год журнала: 2022, Номер 28(29)

Опубликована: Март 18, 2022

Hydrodefluorination (HDF) is a very important fundamental transformation for conversion of the C-F bond into C-H in organic synthesis. In past decade, much progress has been achieved with HDF through utility low-valent metals, transition-metal complexes and main-group Lewis acids. Recently, novel methods have introduced this purpose photo- electrochemical pathways, which are great significance, due to their considerable environmental economical advantages. This Review highlights fluorinated compounds (FOCs) strategies, along mechanistic insights.

Язык: Английский

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