Dienes as Versatile Substrates for Transition Metal‐Catalyzed Reactions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 4, 2024

Abstract Dienes have been of great interest to synthetic chemists as valuable substrates due their abundance and ease synthesis. Their unique stereoelectronic properties enable broad reactivity with a wide range transition metals construct molecular complexity facilitating synthesis biologically active compounds. In addition, structural diene variation can result in substrate‐controlled reactions, providing mechanistic insights into selectivity patterns. The last decade has seen wealth new methodologies involving through the power metal catalysis. This review summarizes recent advances remaining opportunities for metal‐catalyzed transformations dienes.

Язык: Английский

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Unified approaches in transition metal catalyzed C(sp³)–H functionalization: recent advances and mechanistic aspects

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Direct alteration of unactivated C–H bonds organic building blocks.

Язык: Английский

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Язык: Английский

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Cooperative Fe/Co-Catalyzed Remote Desaturation for the Synthesis of Unsaturated Amide Derivatives

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4985 - 4992

Опубликована: Фев. 6, 2024

Unsaturated amides represent common functional groups found in natural products and bioactive molecules serve as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, radical intermediate undergoes hydrogen abstraction from vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated derivatives under mild conditions. efficiency Co-mediated HAT can be tuned varying different auxiliaries, highlighting generality this protocol. Remarkably, desaturation protocol is also amenable to practical scalability, enabling synthesis carbamates ureas, which readily converted into various valuable molecules.

Язык: Английский

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Late‐Stage C−H Activation of Drug (Derivative) Molecules with Pd(ll) Catalysis

Chemistry - A European Journal, Год журнала: 2023, Номер 29(71)

Опубликована: Окт. 17, 2023

Abstract This review comprehensively analyses representative examples of Pd(II)‐catalyzed late‐stage C−H activation reactions and demonstrates their efficacy in converting bonds at multiple positions within drug (derivative) molecules into diverse functional groups. These transformative hold immense potential medicinal chemistry, enabling the efficient selective functionalization specific sites molecules, thereby enhancing pharmacological activity expanding scope candidates. Although notable articles have focused on drug‐like using transition‐metal catalysts, reviews specifically focusing Pd(II) catalysts are required owing to prominence as most widely utilized metal for ability introduce a myriad groups bonds. The utilization Pd‐catalyzed methodologies impressive success introducing various groups, such cyano (CN), fluorine (F), chlorine (Cl), aromatic rings, olefin, alkyl, alkyne, hydroxyl with high regioselectivity functional‐group tolerance. breakthroughs serve invaluable tools discovery development, offering strategic options optimize candidates drive exploration innovative therapeutic solutions.

Язык: Английский

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Ligand‐Enabled Double γ‐C(sp³)−H Functionalization of Aliphatic Acids: One‐Step Synthesis of γ‐Arylated γ‐Lactones

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(49)

Опубликована: Окт. 18, 2023

γ-methylene C(sp

Язык: Английский

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Tandem dehydrogenation-olefination-decarboxylation of cycloalkyl carboxylic acids via multifold C–H activation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 25, 2024

Abstract Dehydrogenation chemistry has long been established as a fundamental aspect of organic synthesis, commonly encountered in carbonyl compounds. Transition metal catalysis revolutionized it, with strategies like transfer-dehydrogenation, single electron transfer and C–H activation. These approaches, extended to multiple dehydrogenations, can lead aromatization. Dehydrogenative transformations aliphatic carboxylic acids pose challenges, yet engineered ligands initiate dehydrogenation via activation, though outcomes vary based on substrate structures. Herein, we have developed catalytic system enabling cyclohexane undergo multifold activation furnish olefinated arenes, bypassing lactone formation. This showcases unique reactivity acids, involving tandem dehydrogenation-olefination-decarboxylation-aromatization sequences, validated by control experiments key intermediate isolation. For cyclopentane reluctant aromatization, the facilitates controlled dehydrogenation, providing difunctionalized cyclopentenes through dehydrogenation-olefination-decarboxylation-allylic acyloxylation sequences. transformation expands into diverse molecular entities wide applications, underscoring its importance.

Язык: Английский

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Dehydrogenation of Aromatic Alcohols, Aldehydes, and Ketones Catalyzed by Cu(I) Complexes

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 11, 2025

Herein, we report that binuclear copper complexes used as dehydrogenative catalysts, combined with oxygen an oxidant and 2,2,6,6-tetramethylpiperidinyl-1-oxide (TEMPO) additive, are capable of effectively catalyzing the successive dehydrogenation aromatic propanols to produce α,β-unsaturated aldehydes. This method has advantages high efficiency, simple operation, oxidant. The reaction mechanism continuous was investigated by in situ infrared spectroscopy control experiments. process suggested phenylpropanol first oxidized arylpropanals then underwent α,β-selective carbonyl group yield protocol provides insights into design synthesis efficient catalysts for preparation aldehydes propanols.

Язык: Английский

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Hydrogen Atom Transfer (HAT)-Mediated Remote Desaturation Enabled by Fe/Cr–H Cooperative Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4795 - 4802

Опубликована: Фев. 8, 2024

An iron/chromium system (Fe(OAc)2, CpCr(CO)3H) catalyzes the preparation of β,γ- or γ,δ-unsaturated amides from 1,4,2-dioxazol-5-ones. acyl nitrenoid iron complex seems likely to be responsible for C–H activation. A cascade three H• transfer steps appears involved: (i) abstraction a remote bond by N, (ii) Cr and (iii) radical substituent Cr•. The observed kinetic isotope effects are consistent with proposed mechanism if formation is rate-determining step. Fe/Cr catalysts can also desaturate substituted 1,4,2-dioxazol-5-ones 3,5-dienamides.

Язык: Английский

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Synthesis of 1,5-Diamino-Substituted 1,3-Dienes via Rhodium(II)-Catalyzed Tandem Reactions of 1-Cyclopropylethylarenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 18, 2025

Herein, (E,E)-1,5-diamino-1,3-dienes are stereoselectively synthesized from substituted aryl derivatives via a rhodium(II)-catalyzed C(sp3)-H functionalization involving cascade of cyclopropane ring expansion, cyclobutene formation, to 1,3-diene conversion, and regioselective diamination. Mechanistic studies show this one-pot process proceeds through hydrogen atom transfer (HAT), radical-polar crossover (RPC), elimination, electrocyclic ring-opening, radical addition, underscoring rhodium(II)'s role in radical-mediated catalysis beyond traditional rhodium(II) nitrenoid chemistry.

Язык: Английский

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