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

Gold-Catalyzed Heck Reaction DOI
Vivek W. Bhoyare, E. Daiann Sosa Carrizo, Chetan C. Chintawar

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 8810 - 8816

Published: April 16, 2023

Herein, we report a gold-catalyzed Heck reaction facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis. The elementary organometallic steps such as migratory insertion and β-hydride elimination have been realized in catalytic fashion for first time gold chemistry. present methodology not only overcomes limitations of previously known transition metal-catalyzed reactions requirement specialized substrates formation mixture regioisomeric products result undesirable chain-walking process but also offers complementary regioselectivity compared to other metal

Language: Английский

Citations

56
DFT-Enabled Development of Hemilabile (P∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides DOI

Karim Muratov,

Emil Zaripov, Maxim V. Berezovski

et al.

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

26
Consolidation of the Oxidant‐Free Au(I)/Au(III) Catalysis Enabled by the Hemilabile Ligand Strategy DOI Creative Commons
Pau Font, Hugo Valdés, Xavi Ribas

et al.

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

Citations

20
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

4
L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free AuI/AuIII Catalysis DOI
Pengcheng Gao, Jihong Xu, Tongliang Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 25, 2023

In the last decade, major advances have been made in homogeneous gold catalysis. However, Au

Language: Английский

Citations

41
Ligand-Enabled Gold-Catalyzed C(sp2)–O Cross-Coupling Reactions DOI
Avishek Das, Nitin T. Patil

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(6), P. 3847 - 3853

Published: March 3, 2023

Reported herein is a ligand-enabled gold-catalyzed C(sp2)–O cross-coupling reaction of aryl iodides and aliphatic alcohols. The synthesis variety alkyl ethers including complex biomolecules various medicinally relevant motifs has been achieved to demonstrate the usefulness method. importance gold catalysis highlighted by overcoming selectivity issues that are in general observed for C–O reactions when other transition metals used as catalysts.

Language: Английский

Citations

40
Site-Selective Arylation of Carboxamides from Unprotected Peptides DOI
Weipeng Li, Yu Chen, Yinghan Chen

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(27), P. 14865 - 14873

Published: June 28, 2023

The amidated peptides are an important class of biologically active compounds due to their unique biological properties and wide applications as potential peptide drugs biomarkers. Despite the abundance free amide motifs (Asn, Gln, C-terminal amide) in native peptides, late-stage modification unit naturally occurring remains very rare because intrinsically weak nucleophilicity amides interference multiple competing nucleophilic residues, which generally lead undesired side reactions. Herein, chemoselective arylation unprotected polypeptides has been developed under air atmosphere afford N-aryl bearing various functional motifs. Its success relies on combination gold catalysis silver salt differentiate relative inert among a collection reactive amino acid residues (e.g., -NH2, -OH, -COOH), favoring C-N bond coupling toward over other more groups. Experimental DFT studies reveal crucial role cation, serves transient coordination mask reaction sites, overcoming inherently low reactivity amides. excellent biocompatibility this strategy applied functionalize range complex peptides. application could be further extended labeling stapling.

Language: Английский

Citations

35
Asymmetric gold catalysis enabled by specially designed ligands DOI
Amol B. Gade,

Urvashi Urvashi,

Nitin T. Patil

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1858 - 1895

Published: Jan. 1, 2024

This review is planned to provide a comprehensive overview of the progress made in design and development chiral ligands for asymmetric gold catalysis.

Language: Английский

Citations

13
Gold‐Catalyzed Arylative Cope Rearrangement DOI
Bidisha Paroi, Chayanika Pegu, Manoj V. Mane

et al.

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

11
Ligand‐Enabled Gold‐Catalyzed Cyanation of Organohalides DOI Open Access
Anil Kumar, Nandita Bhattacharya, Manoj V. Mane

et al.

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

9