DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3660 - 3674

Published: Feb. 5, 2024

Ligand-enabled oxidative addition of Csp2-X bonds to Au(I) centers has recently appeared as a valuable strategy for the development catalytic RedOx processes. Several cross-coupling reactions that were previously considered difficult achieve reported lately, thus expanding synthetic potential gold(I) complexes beyond traditional nucleophilic functionalization π-systems. MeDalPhos played an important role in this and, despite several studies on alternative structures, remains, so far, only general ligand such process. We report herein discovery and DFT-enabled structural optimization new family hemilabile (P∧N) ligands can promote aryl iodides gold(I). These flexible ligands, which possess common 2-methylamino heteroaromatic N-donor motif, are structurally electronically tunable, being easily accessible affordable. The corresponding shown outperform reactivity (MeDalPhos)Au(I) series alkoxy- amidoarylations alkenes. Their comparatively higher further highlighted thiotosylation iodides, challenging unreported C–S reaction could not be achieved under classical Pd(0/II) catalysis allows divergent access sulfur derivatives.

Language: Английский

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Consolidation of the Oxidant‐Free Au(I)/Au(III) Catalysis Enabled by the Hemilabile Ligand Strategy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 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.

Language: Английский

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Gold‐Catalyzed Arylative Cope Rearrangement

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 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,

Language: Английский

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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

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

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Gold‐Catalyzed Alkoxy‐Carbonylation of Aryl and Vinyl Iodides

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Herein, for the first time, we disclose gold‐catalyzed alkoxy‐carbonylation of aryl and vinyl iodides utilizing ligand‐enabled Au(I)/Au(III) redox catalysis. The present methodology is found to be general, efficient, employs mild reaction conditions showcases a broad substrate scope even with structurally complex molecules. Density functional theory (DFT) calculations revealed mechanistic pathways distinct from those conventional transition metal‐catalyzed carbonylation reactions.

Language: Английский

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Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes Via Chain Walking

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16337 - 16343

Published: Dec. 6, 2023

Hydroamination of terminal alkenes represents a powerful and well-established way to introduce nitrogenous functionality feedstock chemicals. Remote hydroamination reactions are far less known represent functionalize unactivated C(sp3) centers distal the site alkene. These transformations commonly take place via metal-hydride-mediated chain walking, as such, regioselectivity can be challenging. The remote introduction amides is particular interest due their prevalence in pharmaceuticals. Herein we report Rh(III)-catalyzed hydroamidation procedure position internal alkenes, using dioxazolones amidation reagents i-PrOH hydride source. reaction proceeds with high yield tolerates variety functionality. Regioconvergent synthesis single linear amide from mixture isomeric demonstrated. Key development this was determining that inorganic bases poison catalyst identifying suitable trialkylamine replacement.

Language: Английский

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Homogeneous Gold Catalysis: Development and Recent Advances

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

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Gold-Catalyzed Migratory Insertion of Alkynes

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

Published: April 28, 2025

Language: Английский

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Borenium-Catalyzed ‘Chain Walking’

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

Published: May 13, 2025

Abstract ‘Chain-walking’ chemistry, a catalytic process enabling the functionalization of remote positions in carbon chains, has traditionally relied on transition-metal catalysts to facilitate alkene isomerization and subsequent transformations. This Synpacts article reviews recent advancements hydroboration via chain-walking pathways, highlighting transition-metal-catalyzed strategies for α-, β-, terminal-selective borylation. Additionally, organoboron compounds emerging role borenium species as mimics are discussed. In particular, we highlight our work borenium-catalyzed ‘chain walking’ functionalization, where have unveiled novel metal-free ‘functionalization-then-isomerization’ strategy. 1 Introduction 2 Background 2.1 Transition-Metal-Catalyzed Remote Hydroboration 2.2 Isomerization Organoboron Compound 2.3 Borenium-Catalyzed Internal Alkenes 3 ‘Chain Walking’ 3.1 ‘Boron-Walking’ Strategy Design 3.2 Reaction Scope 3.3 Synthetic Application 3.4 Mechanistic Study 4 Summary Outlook

Language: Английский

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Pd-Catalyzed Migratory 1,1-Cycloannulation Reaction of Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Here, we report a novel strategy for the preparation of diverse heterocycles via Pd-catalyzed migratory 1,1-cycloannulation reaction (MCAR) alkenes. Starting from readily available alkenyl amines and alcohols, this approach allows formation wide range five- to seven-membered azaheterocycles oxaheterocycles with high efficiency good functional group tolerance. The key realization is use 4-iodophenol or 2-iodophenol derivatives where phenolic hydroxyl plays critical role in controlling direction migration ring-size through quinone methide intermediate.

Language: Английский

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