Gold-Catalyzed Heck Reaction

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

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Electrochemical gold-catalysed biocompatible C(sp2)–C(sp) coupling

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(4), P. 338 - 347

Published: Jan. 12, 2023

Language: Английский

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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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Ligand-Enabled Gold-Catalyzed C(sp²)–S Cross-Coupling Reactions

Organic Letters, Journal Year: 2022, Volume and Issue: 24(24), P. 4459 - 4463

Published: June 13, 2022

Herein we report C(sp2)-S cross-coupling reactions of aryl iodides and arylsulfonyl hydrazides under ligand-enabled, Au(I)/Au(III) redox catalysis. This strategy operates mild reaction conditions, requires no prefunctionalized coupling partner, works across several iodides. The utility this protocol is highlighted through the synthesis various medicinally relevant biaryl sulfones. mechanism supported with control experiments, mass spectrometry, NMR studies.

Language: Английский

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L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free Au^I/Au^III Catalysis

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

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Ligand-Enabled Gold-Catalyzed C(sp²)–O Cross-Coupling Reactions

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

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Site-Selective Arylation of Carboxamides from Unprotected Peptides

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

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A Hemilabile NHC‐Gold Complex and its Application to the Redox Neutral 1,2‐Oxyarylation of Feedstock Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 30, 2023

We describe a Au

Language: Английский

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Gold-catalyzed multicomponent reactions

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(9), P. 2359 - 2384

Published: Jan. 1, 2023

Multicomponent reactions (MCRs) have emerged as an important branch in organic synthesis for the creation of complex molecular structures. This review is focused on gold-catalyzed MCRs with a special emphasis recent developments.

Language: Английский

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