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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Ultrafast Au(III)-Mediated Arylation of Cysteine

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12365 - 12374

Published: April 24, 2024

Through mechanistic work and rational design, we have developed the fastest organometallic abiotic Cys bioconjugation. As a result, Au(III) bioconjugation reagents enable selective labeling of moieties down to picomolar concentrations allow for rapid construction complex heterostructures from peptides, proteins, oligonucleotides. This showcases how chemistry can be interfaced with biomolecules lead range reactivities that are largely unmatched by classical organic tools.

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 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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Ligand‐Enabled Gold‐Catalyzed Cyanation of Organohalides

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

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Visible Light/Copper Catalysis-Enabled Arylation and Alkenylation of Phosphorothioates via Site-Selective C–H Thianthrenation

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 24, 2024

An efficient visible light/copper-enabled arylation and alkenylation of phosphorothioates with thianthrenium salts via a C(sp

Language: Английский

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Electronic Effects of Bidentate P,N-Ligands on the Elementary Steps of Au(I)/Au(III) Reactions Relevant to Cross-Coupling Chemistry

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Oxidant-free Au(I)/Au(III)-catalyzed cross-coupling has been recently enabled by the use of bidentate

Language: Английский

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Synthesis of S-alkyl phosphorothioates/phosphorodithioates via ring-opening reaction of sulfonium salts with S₈, H-phosphonates or P₄S₁₀, and alcohols

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(20), P. 5731 - 5740

Published: Jan. 1, 2024

A simple and practical method for the synthesis of S -alkyl phosphorothioates/phosphorodithioates through three-component reaction cyclic sulfonium salts with 8 , H -phosphonates, or P 4 10 alcohols was readily developed.

Language: Английский

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Gold-Catalyzed Cross-Coupling Reactions of Organoiodides with Disulfides: Access to Aryl Sulfides and Vinyl Sulfide Derivatives

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Thioethers and their derivatives play important roles in synthetic chemistry, medicinal materials science. Herein, we report a hemilabile P,N-ligand-assisted gold-catalyzed C-S cross-coupling reaction of organoiodides with disulfides. In this reaction, alkyl or aryl disulfides react smoothly vinyl iodides to afford series sulfide good excellent yields. The robust capabilities thioether synthesis are exemplified by the readily available easily handled reagents as well compatibility wide range functional groups.

Language: Английский

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