Reply to Correspondence on “Unlocking the Chain‐Walking Process in Gold Catalysis” DOI
Vivek W. Bhoyare, E. Daiann Sosa Carrizo, Vincent Gandon

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 137(1)

Опубликована: Ноя. 12, 2024

Abstract We recently reported the gold‐catalyzed Heck and chain‐walking reactions, which utilize migratory insertion, β ‐hydride elimination steps in a catalytic fashion. Budzelaar et al. their correspondence state that these reactions proceed through alkene heteroarylation followed by acid‐mediated cyclization sequence. In response to this correspondence, we have conducted some experiments convinced us product formation solely can not be rationalized based on hetero‐arylation of alkenes under ligand‐enabled Au(I)/Au(III) catalysis.

Язык: Английский

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

Gold-Catalyzed Migratory Insertion of Alkynes DOI
Avishek Das,

Biswajit Biswas,

Vincent Gandon

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 7867 - 7876

Опубликована: Апрель 28, 2025

Язык: Английский

Процитировано

0

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

Prafulla Bera,

Tanmayee Nanda,

Nivrutti B. Barhate

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 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.

Язык: Английский

Процитировано

0

Palladium-Catalyzed Dearomative para-/ortho-Cycloaddition Cascades of N-Allylanilines with 1,4-Enynes and CO via Skeletal Reorganization DOI
Xue Qi, Yang Li,

Ming Hu

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

A selectivity-control approach for palladium-catalyzed dearomative para-/ortho-cycloaddition cascades of aromatic compounds with 1,4-enynes and CO via a skeletal reorganization process to produce polycycle-fused bicyclo[2.2.2]octenes is reported. This mechanistically novel depends on that consists sequence [4 + 2] para-cycloaddition, 3,3-Cope rearrangement, carbon–carbon bond activation/[4 cycloaddition.

Язык: Английский

Процитировано

0

Gold-Catalyzed 1,2-Rearrangement on Benzene Triggered by a Transient Dearomative Claisen Rearrangement DOI

Jiamin He,

Wenjun Liu, Jialin Wang

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

1,2-Migration on arenes represents a powerful transformation, because of its chemical skeleton and exit vector editing ability. However, the corresponding dearomative mediated 1,2-migration arene was ignored for decades, despite tremendous effort being devoted to develop reaction, which mainly capitalized breaking planarity three-dimensional diversification. Here, we report gold-catalyzed 1,2-rearrangement benzene by transient dearomatization high-resonance energy benzene. This functional transposition strategy enabled rapid access several precursors extended π-conjugated molecules, showcasing potential applications in materials sciences.

Язык: Английский

Процитировано

0

Homogeneous Gold Catalysis: Development and Recent Advances DOI
Tapas Adak

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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.

Язык: Английский

Процитировано

0

Gold-Catalyzed Migratory Insertion of Alkynes DOI Creative Commons
Avishek Das,

Biswajit Biswas,

Vincent Gandon

и другие.

Опубликована: Авг. 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.

Язык: Английский

Процитировано

1

Reply to Correspondence on “Unlocking the Chain‐Walking Process in Gold Catalysis” DOI
Vivek W. Bhoyare, E. Daiann Sosa Carrizo, Vincent Gandon

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Ноя. 12, 2024

Abstract We recently reported the gold‐catalyzed Heck and chain‐walking reactions, which utilize migratory insertion, β ‐hydride elimination steps in a catalytic fashion. Budzelaar et al. their correspondence state that these reactions proceed through alkene heteroarylation followed by acid‐mediated cyclization sequence. In response to this correspondence, we have conducted some experiments convinced us product formation solely can not be rationalized based on hetero‐arylation of alkenes under ligand‐enabled Au(I)/Au(III) catalysis.

Язык: Английский

Процитировано

1

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

Процитировано

0