Cited by Thioarylation of Alkynes to Generate Dihydrothiopheniums through Gold(I)/(III)-Catalyzed Cyclization

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

Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play DOI

Fabio Juliá

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4665 - 4680

Published: March 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Language: Английский

Citations

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

Photoinduced gold-catalyzed cross-couplings DOI

Rongnan Yi,

Zijian Zhao,

Wei‐Min He

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111070 - 111070

Published: April 1, 2025

Language: Английский

Citations

Homogeneous Gold Catalysis: Development and Recent Advances DOI

Tapas Adak

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

Published: April 28, 2025

Abstract Gold catalysis has witnessed remarkable advances over the past decade, with numerous insightful reviews chronicling this progress. However, a comprehensive review addressing developments in field during post‐pandemic COVID era remains notably absent. This aims to bridge that gap by providing an in‐depth analysis of recent studies, shedding light on unique properties gold complexes, particularly intriguing aurophilic interactions distinguish chemistry. The systematically explores latest achievements both mono‐ and dinuclear gold‐catalyzed reactions, focus their applications diverse fields, including redox coupling, asymmetric catalysis, photo‐, electrocatalysis. A special emphasis is placed comparative performance catalysts, latter often exhibiting enhanced catalytic efficiency selectivity certain reactions. By integrating mechanistic insights DFT perspectives representative experimental studies from years, highlights significance synthetic chemistry, identifies emerging trends outlines future directions for field.

Language: Английский

Citations

Gold-Catalyzed Migratory Insertion of Alkynes DOI

Avishek Das,

Biswajit Biswas,

Vincent Gandon

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7867 - 7876

Published: April 28, 2025

Language: Английский

Citations

Chelating-Group-Assisted C(sp²)–O Reductive Elimination at the Gold(III) Center DOI

Avishek Das, Sadhana Tripathi, Lisa Roy

et al.

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

Published: May 1, 2025

Herein, we demonstrate chelating-group-assisted C(sp2)-O reductive elimination at gold(III) centers. Detailed stoichiometric studies highlighted the importance of a chelating group for achieving successful C-O elimination, paving way development catalytic version. The mechanistic investigations, including control experiments, 31P NMR, mass spectrometry, and density functional theory (DFT) studies, suggested that synergistic effect ligand creates highly coordinated environment around Au(III) center to facilitate bond-forming reaction.

Language: Английский

Citations

Gold-Catalyzed Deallylative C–S Cross-Coupling Reactions DOI

Prafulla Bera,

Tanmayee Nanda,

Nivrutti B. Barhate

et al.

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

Published: May 1, 2025

Herein, we report the gold-catalyzed deallylative C-S cross-coupling reaction through ligand-enabled Au(I)/Au(III) redox catalysis. One of major challenges in reactions is to prevent catalyst deactivation caused by formation a strong gold-sulfur bond. We discovered that use allyl phenyl sulfide as sulfur surrogate facilitates dynamic equilibrium between cationic Au(I) and Au(I)-sulfide complexes, overcoming gold quenching problem. A detailed mechanistic investigation, including 31P NMR studies, mass analysis, stoichiometric experiments, provided valuable insights into mechanism, which further supported computational studies.

Language: Английский

Citations

Gold-Catalyzed Migratory Insertion of Alkynes DOI

Avishek Das,

Biswajit Biswas,

Vincent Gandon

et al.

Published: Aug. 1, 2024

Herein, for the first time, we disclose migratory insertion of alkynes into Au(III)‒C bonds in a catalytic fashion. Experimental results clearly suggest that pathway predominates over π-activation - finding further supported by Density Functional Theory (DFT) calculations. The observed regioselectivity underscores distinct advantages and complementarity gold catalysis comparison to palladium catalysis.

Language: Английский

Citations

Thioarylation of Alkynes to Generate Dihydrothiopheniums through Gold(I)/(III)-Catalyzed Cyclization–Cross-Coupling DOI

Joseph A. Kaplan,

Jonghyun Won,

Suzanne A. Blum

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 14, 2024

A thioarylation method is developed for the synthesis of 2,3-dihydrothiopheniums through an electrophilic-cyclization-cross-coupling mechanism, harnessing gold(I)/(III) cycle recently MeDalPhosAuCl catalyst. Single-crystal X-ray crystal structural analysis dihydrothiophenium products characterized antiaddition sulfur and Csp

Language: Английский

Citations