Carbonylative transformation of aryl halides and strong bonds via cheap metal catalysts and sustainable technologies

Green Synthesis and Catalysis, Год журнала: 2024, Номер 5(4), С. 211 - 269

Опубликована: Май 6, 2024

The development of catalytic carbonylation reactions has increased considerably. Although many reviews/chapters/books on have been published, summaries cheap metal-catalyzed aryl halides and other chemical bonds with high dissociation energy C-Y (Y = O, N, H) are still very rare. Focusing green sustainable chemistry, this review summarizes discusses the achievements carbonylative transformations (C(sp2)-X) strong based non-expensive metal catalysts (Co, Mn, Mo, Ni, Fe, Cu), photochemical electrochemical systems developed in recent decades.

Язык: Английский

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Recent advances in transition-metal catalyzed directed C–H functionalization with fluorinated building blocks

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(6), С. 1742 - 1775

Опубликована: Янв. 1, 2022

This review focuses on the advances in transition-metal catalyzed reactions with fluorinated building blocks via directed C–H bond activation for construction of diverse organic molecules an insight into probable mechanistic pathway.

Язык: Английский

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Improving the efficiency and sustainability of catalysts for direct arylation polymerization (DArP)

Journal of Polymer Science, Год журнала: 2021, Номер 60(3), С. 393 - 428

Опубликована: Сен. 15, 2021

Abstract In the past decade, direct arylation polymerization (DArP) has rapidly developed as a sustainable synthetic protocol for cost‐effective, atom‐economical preparation of conjugated polymers. By circumventing monomer functionalization with toxic transmetallating reagents such organostannane and organoboron required Stille‐Migita Suzuki‐Miyaura methods, DArP proceeds through metal‐catalyzed CH activation pathway high‐performance polymer materials. This review evaluates development several classes efficient catalysts/catalytic systems from small‐molecule studies to polymerizations, including mechanisms involved in these transformations how they inspire catalyst design defect‐free synthesis. Recent advances developing more first‐row transition metal catalysts are also highlighted, fundamental understanding should motivate pursuit next generation catalytic enable effective environmentally friendly

Язык: Английский

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Recent Advances in First‐Row Transition‐Metal‐Mediated C−H Halogenation of (Hetero)arenes and Alkanes

Asian Journal of Organic Chemistry, Год журнала: 2022, Номер 11(5)

Опубликована: Март 9, 2022

Abstract The ubiquity of carbon halogen bonds in the structural core numerous biomolecules and pharmaceuticals along with their role as synthetic precursors various organic reactions makes halides a crucial class compounds. Consequently, synthesis high regioselectivity is paramount importance chemistry. In nature, selective halogenation achieved by metalloenzymes efficiency involving high‐valent iron‐oxo active species. selectivity halogenating enzymes attracted considerable attention leading to development several biomimetic approaches for C−H halogenation. Moreover, emergence transition metal (TM) catalyzed site‐selective protocols through directed strategies has also been impressive. There significant first row TM despite dominance late metals catalysts this field. But literature, there no up‐to‐date recent review article that consolidates bio‐mimetic well (X=Cl, Br, I) containing organo‐fluorination all first‐row metals. Thus, we got motivated have focused elucidate developments TM‐catalyzed (hetero)arenes alkanes undirected present review. Additionally, covers progresses fluorination methodologies. Altogether, will provide combined overview transition‐metal‐mediated may benefit scientific community towards new methodologies

Язык: Английский

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CH Activation of Cationic Bismuth Amides: Heteroaromaticity, Derivatization, and Lewis Acidity

Inorganic Chemistry, Год журнала: 2021, Номер 60(24), С. 19086 - 19097

Опубликована: Ноя. 24, 2021

Cationization of Bi(NPh2)3 has recently been reported to allow access single- and double-CH activation reactions, followed by selective transformation Bi-C into C-X functional groups (X = electrophile). Here we show that this approach can successfully be transferred a range bismuth amides with two aryl at the nitrogen, Bi(NRaryl2)3. Exchange one nitrogen-bound group for an alkyl substituent gave first example homoleptic amide mixed aryl/alkyl substitution pattern Bi(NPhiPr)3. This compound is susceptible N-N radical coupling in its neutral form also undergoes CH when transformed cationic species. The second blocked due absence moiety nitrogen. Lewis acidity compared species "[Bi(aryl)(amide)(L)n]+" "[Bi(aryl)2(L)n]+" based on (modified) Gutmann-Beckett method (L tetrahydrofuran or pyridine). heteroaromatic character [Bi(C6H3R)2NH(triflate)] compounds, which are iso-valence-electronic anthracene, investigated theoretical methods. Analytical methods used work include nuclear magnetic resonance spectroscopy, single-crystal X-ray diffraction, mass spectrometry, density theory calculations.

Язык: Английский

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Rh(III)‐Catalyzed C‐H Cyclization of 2‐Arylbenzimidazoles with CF3‐Imidoyl Sulfoxonium Ylides and Further Sc(III)‐Catalyzed Deaminative Hydroxylation

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 16, 2024

Abstract An efficient Rh(III)‐catalyzed C−H bond activation/cyclization of 2‐arylbenzimidazoles with CF 3 ‐imidoyl sulfoxonium ylides has been achieved, yielding diverse − and amino‐disubstituted 5,6‐dihydrobenzoimidazo[2,1‐ a ]isoquinolines, which could undergo deaminative hydroxylation to access hydroxy‐disubstituted ]isoquinolines catalyzed by Sc(OTf) . This developed strategy features easily available starting materials, broad substrate scope, good scalability high efficiency. Moreover, the antitumor activities selected products against some human cancer cell lines were also investigated, results indicated that several show antiproliferative activities.

Язык: Английский

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Synthesis of CF3-Indazoles via Rh(III)-Catalyzed C-H [4+1] Annulation of Azobenzenes with CF3-Imidoyl Sulfoxonium Ylides

Molecules, Год журнала: 2025, Номер 30(1), С. 183 - 183

Опубликована: Янв. 5, 2025

An efficient Rh(III)-catalyzed C-H activation of azobenzenes and subsequent [4+1] cascade annulation with CF3-imidoyl sulfoxonium ylides was developed, yielding diverse CF3-indazoles. This protocol featured easily available starting materials, excellent functional group tolerance high efficiency. Moreover, the antitumor activities selected CF3-indazoles against human cancer cell lines were also studied, results indicated that several compounds displayed considerable antiproliferative activities.

Язык: Английский

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Recent Advances in Transition-Metal Catalyzed C—H Bond Activation for the Synthesis of C(sp³)-Fluoroalkyl Compounds

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(2), С. 516 - 516

Опубликована: Янв. 1, 2025

Язык: Английский

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Insights into the mechanism of 3d transition-metal-catalyzed directed C(sp³)–H bond functionalization reactions

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review provides an overview of the research advaces in Ni-, Cu-, Fe- and Co-catalyzed directed C(sp 3 )–H bond functionalization reactions; including design principles, mechanistic discussions, along with potential applications limitations.

Язык: Английский

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Access to π-Extended Heterocycles Containing Pyrrolo-Coumarin Cores Involving −COCH₃ as a Traceless Directing Group and Materializing Two Successive sp²C–H/sp³N–H and sp²C–H/sp²N–H Activations

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(17), С. 11443 - 11456

Опубликована: Авг. 24, 2022

An efficient protocol has been developed for the preparation of π-extended N-heterocycles involving a Rh(III)-catalyzed C-H activation reaction starting from 3-acetamidocoumarins and internal alkynes. The isolation intermediate pyrrolo-coumarin suggests that -COCH3 group in acetamidocoumarins performs role traceless directing group. Besides, use commercially available [Cp*RhCl2]2 adds more importance as no additional modification catalyst is required. A two-step bearing can be further functionalized to highly decorated heterocyclic moieties materializing sp2 N-H coupling. Moreover, one compounds (3da) capable differentiating between Cr(III) Cr(VI) ions revealed via fluorescence spectroscopy. In addition, spirocyclic N-heterocycles.

Язык: Английский

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