Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13210 - 13225

Published: May 6, 2024

A new class of photoswitchable NHC ligands, named azImBA, has been developed by integrating azobenzene into a previously unreported imidazobenzoxazol-1-ylidene framework. These rigid photochromic carbenes enable precise control over confinement around metal's coordination sphere. As model system, gold(I) complexes these NHCs exhibit efficient bidirectional E–Z isomerization under visible light, offering versatile platform for reversibly photomodulating the reactivity organogold species. Comprehensive kinetic studies protodeauration reaction reveal rate differences up to 2 orders magnitude between E and Z isomers NHCs, resulting in quasi-complete visible-light-gated ON/OFF switchable system. Such high level photomodulation efficiency is unprecedented gold complexes, challenging current state-of-the-art organometallics. Thorough investigations ligand properties paired with structure–reactivity correlations underscored unique ligand's steric features as key factor reactivity. This effective photocontrol strategy was further validated catalysis, enabling situ photoswitching catalytic activity intramolecular hydroalkoxylation -amination alkynes. Given significance findings its potential widely applicable, easily customizable ancillary platform, azImBA poised stimulate development adaptive, multifunctional metal complexes.

Language: Английский

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Evans’ Chiral Auxiliary‐Based Asymmetric Synthetic Methodology and Its Modern Extensions

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 27(4)

Published: Nov. 21, 2023

Abstract Although the asymmetric catalysis has made a spurt of progress, use chiral auxiliaries remains crucial in synthesis due to both reliability and versatility methods, predictability stereochemistry reactions. Up date, Evans’ non‐racemic oxazolidinone‐based synthetic methodology is still widely used synthesis. More importantly, Evans turned out be fruitful source inspiration for development related methodologies. However, although reviews on application organic medicinal chemistry continually appear literature, comprehensive review dedicating extensions elusive. In this review, we summarize methodology, which cover: (1) modification oxazolidinone auxiliaries; (2) extension aldol reaction from syn ‐aldol other diastereomeric adducts; (3) types; (4) imide‐type substrates N ‐alkenyl, ‐allenenyl ‐alkynyl oxazolidinones; (5) achiral catalysis; (6) catalytic transformation products; (7) straightforward transformations products classes compounds than carboxylic acids, esters, alcohols, Weinreb amides.

Language: Английский

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Fluorinated Biphenyl Phosphine Ligands for Accelerated [Au(I)]-Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6128 - 6136

Published: April 8, 2024

Fluorinated JohnPhos-type ligands are proposed as accelerating tools in homogeneous gold(I) catalysis, with PedroPhosAuCl (Cat1) the most efficient one. The well corresponding gold complexes were synthesized high yields and fully characterized also via single-crystal X-ray diffraction. A secondary interaction between distal phenyl ring of phosphane ligand metal center is identified key for fine-tuning overall catalytic performance complexes. In particular, kinetic computational analysis revealed that by accommodating F atoms on biphenyl pendant ligand, more reactive organo-gold intermediates realized toward subsequent nucleophilic condensations. gold-catalyzed indole-hydroarylation 1,6-enynes intramolecular hydroindolynation alkynes have been adopted benchmark reactions to exemplify these effects.

Language: Английский

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Homogeneous Gold Catalysis: Development and Recent Advances

Chemistry - 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

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Recent Advances in the Development of Enantiopure BODIPYs and Some Related Enantiomeric Compounds

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

During the process of developing smart chiroptical luminophores, BODIPYs have emerged as candidates utmost importance. Here in we will discuss their synthesis.

Language: Английский

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Microporous Polymeric Networks Containing a Long-Term Stable Au^I Catalyst for Enyne Cyclization

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(5), P. 2453 - 2463

Published: Feb. 15, 2024

Two microporous polymer networks having a confined AuI carbene catalyst were obtained and tested for the skeletal rearrangement of enynes. These catalysts from precursor porous organic polymers (POPs), type network, synthesized by reaction isatin or mixture isatin/trifluoroacetophenone (1:1) with triptycene (POP1 POP2, respectively) through an electrophilic aromatic substitution, EAS, promoted trifluoromethanesulfonic acid. precursors could be easily functionalized lactam moiety to form (POP1-AuCarbene POP2-AuCarbene). The carbenes proved very active dimethyl 2-(3-methyl-2-butenyl)-2-propinylmalonate enyne. A large increase in stability was observed compared those most homogeneous described so far bibliography. This long-term associated separation atoms, induced their confinement networks. In particular, POP2-AuCarbene exhibited outstanding stability, maintaining catalytic activity even after several months.

Language: Английский

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Three-Component Gold(I)-Catalyzed Alkoxyvinylation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(30), P. 6375 - 6379

Published: July 18, 2024

Acetylene has been underexploited despite being a highly valuable feedstock for chemical synthesis. We have developed the first true gold(I)-catalyzed intermolecular three-component reaction between acetylene, alkenes, and alcohols to afford β-vinyl hemiaminal scaffolds from N-vinyl amides. Unusual biscyclopropyl 3-vinyl N-heterocyclic were obtained through incorporation of second unit or tethered alkene into starting material.

Language: Английский

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Gold/HNTf₂-Cocatalyzed Asymmetric Annulation of Diazo-Alkynes: Divergent Construction of Atropisomeric Biaryls and Arylquinones

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 30, 2024

Due to the inherent challenges posed by linear coordination of gold(I) complexes, asymmetric gold-catalyzed processes remain challenging, particularly in atroposelective synthesis axially chiral skeletons. Except for extremely few examples intramolecular annulations, construction axial chirality via intermolecular alkyne transformation is still undeveloped. Herein, a gold/HNTf

Language: Английский

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Electrochemical Selenocyclization of N-(2-Alkyle)Anilines: Access to 3-Selenylquinolines

Published: Jan. 1, 2024

Language: Английский

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Electrochemical Selenocyclization of N-Alkyl anilines: Access to 3-Selenyl quinolines

Tetrahedron, Journal Year: 2024, Volume and Issue: unknown, P. 134257 - 134257

Published: Sept. 1, 2024

Language: Английский

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