Gold bulletin, Journal Year: 2023, Volume and Issue: 56(4), P. 159 - 165
Published: Dec. 1, 2023
Language: Английский
Gold bulletin, Journal Year: 2023, Volume and Issue: 56(4), P. 159 - 165
Published: Dec. 1, 2023
Language: Английский
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
Citations
23Angewandte 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
Citations
17Angewandte 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
Citations
8ACS 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
Citations
12Organic 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
0Chemistry - 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
0ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7867 - 7876
Published: April 28, 2025
Language: Английский
Citations
0Angewandte 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
Citations
3Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(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
Citations
2Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 14, 2024
Language: Английский
Citations
2