Computational Mechanistic Elucidation of C–N Cross-Coupling Reactions via Ligand-Enabled Au(I)/Au(III) Catalysis: Insights into Y-Arylation of Y–H Bonds (Y = N, C, O, S) Under Base-Free Conditions DOI
Leyla Mohammadkhani, Ye zhang, Robert Stranger

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(21), P. 2831 - 2842

Published: Oct. 29, 2024

Arylation of Y–H bonds (Y = N, C, O, S) catalyzed by transition metal complexes typically requires an external base to deprotonate the bonds, thereby preparing system for Y-aryl coupling. However, designing catalytic reactions that operate without bases is preferred due benefits such as simplicity, cost savings, and reduced environmental impact. In this study, we demonstrate substrates with can undergo Y-arylation under base-free conditions if their coordination center renders them sufficiently acidic deprotonation solvent. We identified several reports in literature meet criterion, including arylation anilines 1,3,5-trimethoxybenzene using hemilabile ligand-enabled Au(I)/Au(III) catalysis methanol. Our density functional theory (DFT) calculations reveal key intermediate Au(III)-substrate adduct. The success depends on acidity (pKa) adduct, which significantly influenced substrate substituents. For example, our indicate pKa values Au(III)-coordinated p-nitroaniline methanol are 2.1 4.6, respectively. These adducts thus be easily deprotonated solvent, enabling conditions.

Language: Английский

Photosensitized Gold-Catalyzed Cross-Couplings of Aryl Bromides DOI
Jiawen Wu,

Fusheng Guo,

Chenju Yi

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

Recently, ligand-promoted Au(I)/Au(III)-catalyzed cross-coupling reactions with aryl iodides have garnered considerable attention. Here, we report the first visible-light-driven gold-catalyzed cross-couplings of challenging bromides. In presence a (P, N)-gold(I) catalyst and an acridinium photocatalyst under blue LED irradiation, C-O coupling bromides carboxylic acids was achieved, soon it found that this photoinduced appliable for other C-C, C-N, C-S bond formation. Experimental computational studies suggest involves two discrete energy transfer (EnT) events: first, from photosensitizer produces excited-state gold(I) complex allows bottleneck oxidative addition to form Au(III) second, reductive elimination aryl-Au(III) regenerate Au(I). Collectively, new synergistic catalytic method developed here highlights tremendous potential photochemical gold catalysis via organogold complexes, as well its facilitate drug discovery due biocompatibility mildness reaction conditions.

Language: Английский

Citations

1
Electrochemical Gold Redox Catalysis DOI
Anil Kumar, Nandita Bhattacharya, Nitin T. Patil

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 29, 2024

Abstract The high oxidation potential of Au(I)/Au(III) redox couple renders the development gold‐catalyzed cross‐coupling reactions highly challenging. In pursuit catalysis, various strategies, such as use stoichiometric oxidants, merged gold/photoredox systems, or ligand‐enabled approaches, have been adopted to achieve Au(I) Au(III) complexes. Recently, electrochemical anodic oxidation‐based gold catalysis has emerged a new technique facilitate reactions. This concept article provides succinct overview highlighting challenges and future developments.

Language: Английский

Citations

6
Ligand‐Enabled Gold‐Catalyzed Cyanation of Organohalides DOI Open Access
Anil Kumar, Nandita Bhattacharya, Manoj V. Mane

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 12, 2024

Abstract Herein, we disclose the first report on gold‐catalyzed C(sp 2 )‐CN cross‐coupling reaction by employing a ligand‐enabled Au(I)/Au(III) redox catalysis. This transformation utilizes acetone cyanohydrin as nucleophilic cyanide source to convert simple aryl and alkenyl iodides into corresponding nitriles. Combined experimental computational studies highlighted crucial role of cationic silver salts in activating stable (P,N)‐AuCN complex towards oxidative addition subsequently generate key aryl‐Au(III) complexes.

Language: Английский

Citations

6
Electronic Effects of Bidentate P,N-Ligands on the Elementary Steps of Au(I)/Au(III) Reactions Relevant to Cross-Coupling Chemistry DOI Creative Commons
Joseph W. Treacy, Elaine Y. Chao, Grace E. Kunkel

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Oxidant-free Au(I)/Au(III)-catalyzed cross-coupling has been recently enabled by the use of bidentate

Language: Английский

Citations

4
Electrochemistry and Gold Catalysis: Unusual Allies in Redox Mediated Organic Reactions DOI Open Access
Chandrasekar Praveen, Giuliano C. Clososki

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

Devising advanced protocols to avoid harsh oxidants is of paramount interest in gold catalyzed redox reactions. To address this issue, electrochemical oxidation precatalytic AuI complexes catalytically active AuIII situ species has started emerge as a potential alternative. Such endeavours not only unlocked the possibility direct anodic AuIII, but also enables stepwise AuII through mediation electro-generated organic radicals. Induction these apt events opened gates for several cross-coupling and cyclization Therefore, prime focus review summarize foundational studies laid on electro-redox strategies oxidant-free Wherever required, we covered insightful discussions limited examples by correlating role electrolytes, catalysts, electrodes, solvents contributing reactivity well selectivity such

Language: Английский

Citations

0
Gold-Catalyzed 1,2-Carboxyarylation of Alkenes DOI
Tanmayee Nanda, Avishek Das, Prafulla Bera

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 24, 2025

Herein, we disclose an unprecedented gold-catalyzed 1,2-carboxyarylation of alkenes through ligand-enabled Au(I)/Au(III) catalysis. Unlike other approaches for the arylative functionalization C-C multiple bonds, attempts to utilize weak nucleophiles such as carboxylate anions were unsuccessful. The key achieving this transformation is use a 1,3-diketone-appended alkene, which undergoes oxyarylation followed by retro-aldol reaction afford product. Detailed mechanistic investigations conducted support proposed mechanism.

Language: Английский

Citations

0
Interrogating the anti-Insertion of Alkynes into Gold(III) DOI Creative Commons
Jaime Martín, Johannes Schörgenhumer, Cristina Nevado

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(3), P. 1439 - 1447

Published: Feb. 26, 2025

Alkyne hydrofunctionalizations are a powerful strategy to efficiently build up structural complexity. The selectivity of these reactions is typically governed by the interaction between alkyne and metal-hydride, which commonly proceeds via well-understood syn-insertion mechanism. In contrast, anti-insertions far less common, with proposed mechanisms often extrapolated from literature precedents rather than grounded in direct experimental evidence. While gold complexes rank among most efficient catalysts for such transformations, mechanistic understanding key insertion step remains incomplete. this study, we demonstrate that stable gold(III)-hydrides, featuring (P∧N∧C) ligand, undergo selective alkynes yield corresponding anti-Markovnikov Z-vinyl complexes. A combination control experiments, kinetic studies, computational analyses reveals nonradical, bimolecular process, water plays pivotal role accelerating reaction potentially stabilizing highly reactive, T-shaped gold(I) intermediate. Notably, first demonstration both activated unactivated terminal internal into gold(III)-hydride complex.

Language: Английский

Citations

0
Gold-Catalyzed Difunctionalization of Activated Alkynes with Organohalides: Access to 3-Arylated and Alkenylated Coumarin Derivatives DOI

Yu Zhong,

Yuanhao He,

Yan-Fei Hu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Coumarin skeletons are significant structural units frequently used in the fields of synthetic chemistry, medicinal and materials science. Herein, we report a hemilabile P,N-ligand-assisted gold-catalyzed difunctionalization activated alkynes with organohalides. The reaction occurs effectively under mild conditions without requiring an external oxidant, producing variety 3-arylated alkenylated coumarin derivatives high to excellent yields. This method demonstrates wide substrate tolerance superb functional group compatibility is also suitable for heteroaromatic substrates. Further mechanistic investigations strongly support proposed mechanism reaction.

Language: Английский

Citations

0
Exploring the Electronic and Steric Effects of Hemilabile (P^N) Ligands in Redox Gold Catalysis: Application to the Cross-Coupling Reaction of Aliphatic Amines with Aryl Iodides DOI

Urvashi Urvashi,

Saurabh Rai, Gaurav Shukla

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

Herein, we report 17 new (P^N) ligands for redox gold catalysis, featuring various substituents at -C4, -C5, and -C6 of the aryl ring nitrogen handle. Rate kinetics experiments revealed that electron-rich -C4 -C5 positions enhanced rate oxidative addition Au(I) with C(sp2)-Br bonds compared to electron-poor substituents. Further, an unprecedented gold-catalyzed arylation aliphatic amines using electronically rich ligand (L6) -OMe group position.

Language: Английский

Citations

0
Gold‐Catalyzed Alkyne‐Amine Cascade Annulations: A Modern Strategy for Azaheterocycle Construction DOI
Alexey Yu. Dubovtsev

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Abstract Gold catalysis has experienced remarkable progress over the past two decades, particularly in transformations involving alkynes. While numerous aspects of gold‐catalyzed reactions have been extensively reviewed, specific area cascade annulations between functionalized amines and alkynes represents a distinct rapidly developing direction that warrants focused attention. This survey collects systematically analyzes these transformations, which emerged as convenient synthetic strategies to diverse nitrogen heterocycles. The relevant are classified firstly by chemical nature amine functional substituent, secondly size formed ring. field under consideration bridges several fundamental practical branches chemistry, including catalysis, organic synthesis, medicinal materials science.

Language: Английский

Citations

0