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

и другие.

Organometallics, Год журнала: 2024, Номер 43(21), С. 2831 - 2842

Опубликована: Окт. 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.

Язык: Английский

Consolidation of the Oxidant‐Free Au(I)/Au(III) Catalysis Enabled by the Hemilabile Ligand Strategy DOI Creative Commons
Pau Font, Hugo Valdés, Xavi Ribas

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(27)

Опубликована: Апрель 30, 2024

Abstract In this minireview we survey the challenges and strategies in gold redox catalysis. Gold's reluctance to oxidative addition reactions due its high potential limits applicability. Initial attempts overcome problem focused on use of sacrificial external oxidants stoichiometric amounts bring Au(I) compounds Au(III) reactive species. Recently, innovative approaches employing hemilabile ligands, which are capable coordinating stabilizing square‐planar intermediates, thus facilitating steps enabling oxidant‐free Notable examples include (P^N) bidendate MeDalphos ligand achieve various cross‐coupling via Au(I)/Au(III). Importantly, ligand‐enabled catalysis allows merging with π‐activation, such as oxy‐ aminoarylation alkenols alkenamines using organohalides, expanding gold‘s versatility C−C C‐heteroatom bond formations unprecedented cyclizations. Moreover, recent advancements enantioselective chiral ligands also surveyed. Strikingly, versatile bidentate (C^N) competitors have appeared recently, by designing scaffolds where phosphine groups substituted N‐heterocyclic or mesoionic carbenes. Overall, these highlight evolving landscape tremendous a broad scope transformations.

Язык: Английский

Процитировано

22

Ultrafast Au(III)-Mediated Arylation of Cysteine DOI
Evan A. Doud, James A. R. Tilden, Joseph W. Treacy

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12365 - 12374

Опубликована: Апрель 24, 2024

Through mechanistic work and rational design, we have developed the fastest organometallic abiotic Cys bioconjugation. As a result, Au(III) bioconjugation reagents enable selective labeling of moieties down to picomolar concentrations allow for rapid construction complex heterostructures from peptides, proteins, oligonucleotides. This showcases how chemistry can be interfaced with biomolecules lead range reactivities that are largely unmatched by classical organic tools.

Язык: Английский

Процитировано

19

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

Fusheng Guo,

Chenju Yi

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

Процитировано

4

Gold‐Catalyzed Arylative Cope Rearrangement DOI
Bidisha Paroi, Chayanika Pegu, Manoj V. Mane

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Май 21, 2024

Cope rearrangements have garnered significant attention owing to their ability undergo structural reorganization in stereoselective manner. While substantial advances been achieved over decades, these remained applicable exclusively parent 1,5-hexadienes. Herein, we disclose the gold-catalyzed arylative rearrangement of 1,6-heptadienes via a cyclization-induced [3,3]-rearrangement employing ligand-enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross-over experiment, HRMS analysis,

Язык: Английский

Процитировано

11

In Silico Screening of P,N-Ligands Facilitates Optimization of Au(III)-Mediated S-Arylation DOI Creative Commons
Joseph W. Treacy, James A. R. Tilden, Elaine Y. Chao

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

In silico examination of 13 P , N -ligated Au( iii ) OACs determined the key mechanistic factors governing )-mediated S -arylation. Three complexes were synthesized which exhibited bimolecular coordination rate constants as high 20 200 M −1 s .

Язык: Английский

Процитировано

2

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

и другие.

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Июль 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.

Язык: Английский

Процитировано

9

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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(47)

Опубликована: Авг. 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.

Язык: Английский

Процитировано

9

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

Prafulla Bera

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

Процитировано

1

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

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

Процитировано

1

Ligand-Enabled Oxidative Fluorination of Gold(I) and Light-Induced Aryl–F Coupling at Gold(III) DOI

David Vesseur,

Shuo Li, Sonia Mallet‐Ladeira

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Апрель 12, 2024

MeDalphos Au(I) complexes featuring aryl, alkynyl, and alkyl groups readily react with electrophilic fluorinating reagents such as

Язык: Английский

Процитировано

6