Iron/Photosensitizer-Catalyzed Directed C–H Activation Triggered by the Formation of an Iron Metallacycle

ACS Catalysis, Год журнала: 2023, Номер 13(7), С. 4552 - 4559

Опубликована: Март 21, 2023

C–H functionalization reactions catalyzed by iron, the most abundant transition metallic element in Earth's crust, are one of ideal synthetic methods. However, there a limited number strategies for iron-catalyzed directed activation when compared to other first-row metals. Here, we report iron/photosensitizer-catalyzed alkenylation amide derivatives via σ-CAM (σ-complex-assisted metathesis) promoted situ generation an iron metallacycle. Mechanistic experiments suggest that bond cleavage would proceed from metallacycle generated rather than oxidative addition low-valent species.

Язык: Английский

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Modern Organometallic C−H Functionalizations with Earth‐Abundant Iron Catalysts: An Update

Chemistry - An Asian Journal, Год журнала: 2023, Номер 19(1)

Опубликована: Дек. 5, 2023

Abstract Iron‐catalyzed C−H activation has recently emerged as an increasingly powerful synthetic method for the step‐ and atom‐ economical direct functionalizations of otherwise inert bonds. Iron's low‐cost toxicity along with its catalytic versatility have encouraged scientific community to elect this metal development new methodologies. Within review, we aim present a collection most recent examples iron‐catalyzed particular emphasis on modern strategies mechanistic aspects.

Язык: Английский

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C−H Functionalization of Aldehydes and Ketones with Transient Directing Groups: Recent Developments

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(31)

Опубликована: Июль 4, 2023

Abstract In order to directly functionalize C−H bonds of complex molecules and, in particular, control the regioselectivity reaction, a wide range directing groups has been used. However, these need be installed and removed for further applications, which may limit use activation synthesis. Concerning aldehydes ketones, transient group strategy recently emerged overcome this drawback. The addition an additive, general amine, allowed situ formation real achieve activation. This review presents latest developments field over period 2020–2023.

Язык: Английский

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Ni‐SPO‐Al Catalyzed Stereoselective C–H Alkenylation of Quinazolinones with Alkynes to Prepare trans‐Isomers

European Journal of Organic Chemistry, Год журнала: 2025, Номер 28(5)

Опубликована: Янв. 4, 2025

Abstract A stereoselective Ni−Al bimetal‐catalyzed C−H alkenylation of quinazolinones with alkynes has been successfully developed. Good selectivity Z‐type quinazolinone products was obtained using readily available substrates, which exhibits a trans‐configuration opposite to the conventional alkynylation reactions and improves diversity compounds. In addition, reaction process further explored through KIE other control experiments, possible mechanism proposed.

Язык: Английский

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The fun of challenging something different from others

Journal of Synthetic Organic Chemistry Japan, Год журнала: 2025, Номер 83(1), С. 63 - 67

Опубликована: Янв. 1, 2025

Язык: Английский

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N-heterocyclic iminium ions catalyzed Friedel–Crafts type alkenylation of arenes with alkynes: A metal free and solvent free approach

Catalysis Communications, Год журнала: 2023, Номер 182, С. 106753 - 106753

Опубликована: Авг. 23, 2023

The current manuscript elucidates a pioneering approach for achieving regioselective Markovnikov-type hydroarylation of alkynes, without the use any metal catalysts. aforementioned process is expedited through implementation 2-amino-perimidinium bromide and TFA as catalyst systems executed in absence solvents, thereby expanding range substrates (including arenes alkynes). correlation between stoichiometric reactions experimental data substantiates postulated reaction mechanism.

Язык: Английский

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Mechanism of Iron‐Catalyzed C—H Alkenylation of Pivalophenone Derivatives With Unsymmetric Internal Alkynes

International Journal of Quantum Chemistry, Год журнала: 2024, Номер 124(18)

Опубликована: Сен. 11, 2024

ABSTRACT The mechanism of an iron‐catalyzed C—H alkenylation pivalophenone derivatives with unsymmetric internal alkynes is investigated in details by means density functional theory calculations. It shown that the reaction begins two consecutive ligand exchanges, followed a fast and reversible oxidative addition activation step. Next, alkyne insertion into Fe—H bond, isomerization steps, reductive elimination afford final product. turnover‐limiting step process, also determines regiochemical outcome reaction. origin regioselectivity proposed to be steric repulsion between bulky trimethylsilyl group aromatic fragment leading not observed regioisomer.

Язык: Английский

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Hydroarylative cyclization of enynes with aromatic ketones catalyzed by a low-valent iron-phosphine complex

Tetrahedron Letters, Год журнала: 2024, Номер unknown, С. 155409 - 155409

Опубликована: Дек. 1, 2024

Язык: Английский

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N-Heterocyclic Iminium Ions Catalyzed Friedel–Crafts Type Alkenylation of Arenes with Alkynes: A Metal Free and Solvent Free Approach

Опубликована: Янв. 1, 2023

The current manuscript elucidates a pioneering approach for achieving regioselective Markovnikov-type hydroarylation of alkynes, without the use any metal catalysts. aforementioned process is expedited through implementation 2-amino-perimidinium bromide (class N-heterocyclic iminium ions) and TFA as catalyst systems executed in absence solvents, thereby expanding range substrates (including arenes alkynes). correlation between stoichiometric reactions experimental data substantiates postulated reaction mechanism.

Язык: Английский

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Catalytic Addition of C–H Bonds Across C–C π-Bonds

Elsevier eBooks, Год журнала: 2023, Номер unknown

Опубликована: Янв. 1, 2023

Язык: Английский

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