Published: Sept. 4, 2023
Reported herein is the gold-catalyzed alkenylation and arylation of phosphorothioates using alkenyl aryl iodides. The facile transmetalation between Ag-sulfur complex Au(III) intermediate formed after oxidative addition key to success this transformation. This methodology operates under mild reaction conditions with catalyst loading as low 1 mol%, thereby providing an efficient access biologically active S-alkenyl S-aryl
Language: Английский
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
4
Chemical Science, Journal Year: 2023, Volume and Issue: 14(45), P. 13134 - 13139
Published: Jan. 1, 2023
Reported herein is the ligand-enabled gold-catalyzed alkenylation and arylation of phosphorothioates using alkenyl aryl iodides. Mechanistic studies revealed a crucial role in situ generated Ag-sulfur complex, which undergoes facile transmetalation with Au(iii) intermediate, thereby leading to successful realization present reaction. Moreover, for first time, phosphoroselenoates under gold redox catalysis has been presented.
Language: Английский
Citations
29
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 26, 2025
A photoinduced copper-mediated acyloxylation of arylthianthrenium or arylphenoxathiinium salts with either aliphatic aromatic carboxylic acids is described for the convenient synthesis O-aryl esters. The reaction has shown obvious advantages, such as high efficiency, good functional group tolerance, excellent chemoselectivity, and capacity esterification complex drug molecules, offering a practical synthetic route to multifunctionalized sterically congested esters, which are potentially useful in development new prodrugs twin drugs.
Language: Английский
Citations
1
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
Citations
8
JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 3084 - 3093
Published: July 25, 2024
Compared to the well-established transition metal-catalyzed cross-coupling reactions, Au(I)/Au(III)-catalyzed reactions have lagged behind. Despite some advancements, achieving gold-catalyzed C-O coupling with carboxylic acids via an Au(III) carboxylate intermediate remains challenging due thermal unfavorability of critical reductive elimination step. Here, we present first photosensitized gold(III) enable esterification aryl iodides acids. In presence a (P, N)-gold(I) catalyst and photosensitizer benzophenone under blue LED irradiation, derivatives were obtained from both alkyl (1°, 2°, 3°) Mechanistic modeling studies support that energy transfer (EnT) produces excited-state complex couples This photoinduced energy-transfer strategy has been applied in several other gold catalysis indicating its potential for further applications.
Language: Английский
Citations
6
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)
Published: Aug. 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.
Language: Английский
Citations
6
The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(4), P. 1616 - 1627
Published: Jan. 16, 2025
We herein disclose a visible-light-induced synthesis of O-aryl esters through the cross-dehydrogenative coupling aldehydes with phenols using BrCCl3, in which phenolate functions as both substrate and photosensitizer. This transition-metal- photocatalyst-free esterification is suitable for wide range substrates gives moderate to excellent yields (up 95%). Mechanistic studies provided evidence self-propagating radical reaction involving homolytic cleavage aldehydic C–H bond formation acyl bromides. BrCCl3 serves an oxidant hydrogen atom transfer (HAT) agent.
Language: Английский
Citations
0
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
0
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
0
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
0