Nickel-Catalyzed Selective C–H Cyanation via Aromatic Thianthrenium Salts

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 9249 - 9256

Published: June 23, 2023

Here, we report the first case of nickel-catalyzed C–H cyanation via arylthianthrenium salts. The reaction features use air-stable and inexpensive NiCl2·6H2O as a catalyst for highly selective construction products by aromatic pre-thianthrenation. mechanism study shows that formation aryl radicals is involved. Also, this protocol can be applied to late-stage functionalization bioactive molecules readily scalable, further showcasing synthetic utility.

Language: Английский

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Mechanisms of C(sp³)-H Functionalization of Acetonitrile or Acetone with Alkynes: A DFT Investigation

Journal of Chemical Information and Modeling, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

The mechanisms for the C(sp3)-H activation and addition reactions between acetonitrile (or acetone) alkynes have been investigated with M06-2X-D3/ma-def2-TZVP method basis set. SMD (solvation model based on solute electron density) was applied to simulate solvent effect. In first second reactions, 2-phenylbut-3-yn-2-ol reacted acetone, respectively. First, activations of acetone could be achieved by PhCOO• t-BuO• radicals. Then, converted into final products P1 P2. Gibbs free energy surfaces these two suggest that blue lines would favorable paths lower barriers, terminal C atom C≡C bond is best reactive site. Moreover, analysis IRI (Interaction Region Indicator) reveals Z- E-configuration transformations. While in third fourth methyl(2-(phenylethynyl)phenyl)sulfane has interactions via some paths, profiles show C10 atom, rather than C11 priority, are favorable. Furthermore, action mode Na2HPO4 reduce barrier benefit reaction. vdW (van der Waals) play an important role choice fifth sixth) reaction, it happened 1-(2-(methylthio)phenyl)-3-phenylprop-2-yn-1-one acetontrile yield product P5 P6). computational results uncovered line path, site depends interactions, which origin selectivity. addition, investigation byproducts carried out, can explain reason only main produced. Both those agree experimental results. localized orbital locator (LOL) isosurfaces, Laplacian order (LBO), density critical point (ρBCP), spin isosurface graphs, graphs used analyze structure reveal reaction substances.

Language: Английский

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Catalytic Decarbonylative Functionalization of C–H Bonds with Carboxylic Acids

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Abstract Within the past decades, potential of transition-metal-catalyzed cross-coupling reactions using carboxylic acids as coupling partners has been subjected to extensive exploitation because natural abundance, ready availability, nontoxicity, stability, structural diversity, and low cost acids. Notably, recent years have witnessed intense research interest in combination decarbonylation with direct C–H bond functionalization presence transition-metal catalysts for formation various C–C bonds release CO. The approach presents a powerful alternative existing repertoire via formation. In this Account, we highlight our achievements development decarbonylative under catalysis. 1 Introduction 2 Arylation Aryl Carboxylic Acids 3 Alkenylation Alkenyl 4 Alkylation Alkyl 5 Conclusion Outlook

Language: Английский

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Iron‐Catalyzed Deoxynitrogenation of Carboxylic Acids with Cyanamides to Access Nitriles

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(31)

Published: March 16, 2023

Efficient strategies to access nitriles from common organic functionalities are highly important, given their significance in synthetic and medicinal chemistry. Although the direct transformation of carboxylic acids have been explored for decades, there is few general practical protocol acid precursors. Herein, an iron-catalyzed deoxynitrogenaton strategy convert into described. This method utilizes a cyanamide as recyclable nitrogen donor deoxygenating reagent, operates broadly across aryl, alkenyl, alkyl acids, features easy setup without inert gas protection. The value this demonstrated by application late-stage modification drug molecules, synthesis pharmaceutical structure, scaleup reactions downstream derivatizations.

Language: Английский

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Palladium-Catalyzed Decarbonylative Annulation of 2-Arylbenzoic Acids with Internal Alkynes toward Phenanthrenes

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(17), P. 12808 - 12815

Published: Aug. 17, 2023

A palladium-catalyzed decarbonylative annulation of 2-arylbenzoic acids with internal alkynes via C(sp2)-H activation has been developed. series phenanthrenes were produced in moderate to good yield functional group tolerance. The mechanism study indicated that the should be rate-determining step during reaction.

Language: Английский

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Carboxylic acids as double aryl group donors for biaryl synthesis

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(22), P. 5698 - 5704

Published: Jan. 1, 2023

The synthesis of biaryl compounds by employing carboxylic acids as double aryl group donors is reported.

Language: Английский

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Palladium-Catalyzed Decarbonylative Sonogashira Alkynylation of Carboxylic–Phosphoric Anhydrides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2665 - 2674

Published: Jan. 30, 2024

We report the first palladium-catalyzed decarbonylative alkynylation of carboxylic–phosphoric anhydrides via highly selective C(O)–O bond cleavage. Carboxylic–phosphoric are active carboxylic acid derivatives, which generated through activating acids using phosphates by esterification or direct dehydrogenative coupling with phosphites. Highly valuable internal alkynes have been present method, and efficiency this approach has demonstrated a wide substrate scope excellent functional group tolerance.

Language: Английский

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An efficient platform for decarboxylative functionalization of carboxylic acids using sulfuryl fluoride: Pd-catalyzed decarboxylative dehydrogenation of alkanecarboxylic acids and decarboxylative cross-coupling of arenecarboxylic acids

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4156 - 4167

Published: Jan. 1, 2024

An in situ SO 2 F -mediated and palladium-catalyzed method is shown for the decarboxylative dehydrogenation of alkanecarboxylic acids cross-coupling arenecarboxylic acids, respectively.

Language: Английский

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A one-step base-free synthesis of N-arylamides via modified pivaloyl mixed anhydride mediated amide coupling

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(18), P. 3825 - 3828

Published: Jan. 1, 2023

Pivalic anhydride is shown to be an effective reagent for direct amidation of carboxylic acids with N -alkyl anilines under base-free conditions.

Language: Английский

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Dehydration of Amides by Redox‐Active Phenalenyl Based Mn‐Catalyst

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(19)

Published: Aug. 8, 2023

Abstract A redox‐active phenalenyl ligand coordinated Mn(III)‐complex can be reduced chemically to generate an active catalyst containing a ligand‐centered radical. This Mn‐catalyst shows excellent catalytic reactivity for silylative dehydration of wide range primary amides (including late‐stage diversification various bio‐active molecules) synthesize nitriles using inert and inexpensive silane, polymethylhydrosiloxane (PMHS), under mild conditions. Control experiments suggest radical pathway the present reaction, initiated by

Language: Английский

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