%V_Bur index and steric maps: from predictive catalysis to machine learning

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 853 - 882

Published: Dec. 19, 2023

Steric indices are parameters used in chemistry to describe the spatial arrangement of atoms or groups molecules.

Language: Английский

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Asymmetric gold catalysis enabled by specially designed ligands

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

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Gold(I) N‐heterocyclic carbene (NHC) complexes containing 6‐mercaptopurine derivatives and their in vitro anticancer and anti‐inflammatory effects

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 38(4)

Published: Feb. 22, 2024

A series of eight N ‐heterocyclic carbenes (NHC) gold(I) complexes, involving 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (iPr) ligand in combination with 6‐mercaptopurine derivatives (HL 1–8 ), has been prepared and thoroughly characterized, including elemental analysis, mass spectrometry, infrared multinuclear NMR spectroscopy, single crystal X‐ray analysis. The showing general composition [Au (iPr)(L n )] 1 – 8 , were evaluated for their vitro cytotoxicity against four human cancer cell lines A2780 (ovarian) A2780R (ovarian Cisplatin resistant), PC3 (prostate) MCF‐7 (breast), normal MRC‐5 cells (lung fibroblasts). complexes revealed significant cytotoxicity, the best IC 50 values ≈ 3.4–6.4 μM reasonable selectivity. Cellular effects selected on using various flow cytometry assays. Complexes 3 4 showed a strong pro‐apoptotic effect loss mitochondrial membrane potential. These findings indicate that major mechanism action is based collapse metabolism activation intrinsic signaling pathway apoptosis, consequently resulting death. only negligible production inflammatory‐related cytokine (TNF‐α), as well nuclear factor kappa‐light‐chain‐enhancer activated B (NF‐κB) or peroxisome proliferator‐activated receptor gamma (PPARγ). Moreover, shotgun proteomic analysis was performed, obtained results suggest differs somewhat from Auranofin .

Language: Английский

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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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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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AuIII Acyclic (Amino)(N-Pyridinium)carbenoids: Synthesis via Addition of 2-PySeCl to AuI-Bound Isonitriles, Structures, and Cytotoxicity

International Journal of Molecular Sciences, Journal Year: 2025, Volume and Issue: 26(2), P. 483 - 483

Published: Jan. 8, 2025

In this study, we report the first example of acyclic (amino)(N-pyridinium)carbenoid gold(III) complexes synthesized via a coupling reaction between 2-pyridylselenyl chloride and Au(I)-bound isonitriles. The involves an initial oxidative addition Se-Cl moiety to Au(I), followed by nucleophilic pyridine fragment isonitrile's C≡N bond, furnishing metallacycle. Importantly, is acting as nucleophile towards metal-bound Arguably, such due chelate effect. structures carbenoid were unambiguously established using X-ray diffraction NMR spectroscopy. Theoretical calculations, including DFT, Natural Resonance Theory (NRT), Meyer bond order (MBO) analyses, used analyze different resonance forms. mechanism was further elucidated DFT which identified rate-determining step with barrier 29.7 kcal/mol. proceeds minimal barrier, making highly favorable. antiproliferative activity new compounds 2a-2e tested against two human cancer cell lines: A2780 ovarian adenocarcinoma A278Cis cisplatin-resistant variant.

Language: Английский

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Practical Synthesis of Chiral Ferrocenenylphosphino-Gold(I) Catalysts and NEST Analysis of the Enantioinduction

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2342 - 2350

Published: Jan. 24, 2025

The concise modular synthesis of a family monodentate 1,2-disubstituted ferrocene ligands containing diaryl phosphine and 2-aryl indole is described. Their gold(I) complexes were applied to the enantioselective gold(I)-catalyzed formal [4 + 2] cycloaddition 1,6-arylenynes, enyne cyclization/nucleophile addition N-tethered 1,6-enynes, methoxycyclization 1,6-arylenynes with high levels enantioselectivity in all cases. Crystallographic computational studies highlighted relevant role noncovalent interactions within ligand scaffold between substrate modes enantioinduction cyclization unsaturated substrates. Our recently developed open-source tool NEST was analyze chiral pockets catalysts, which combination RDKit allowed us understand these reactions, paving way for predictive-based approach toward rational development Au(I) catalysis.

Language: Английский

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Stable cyclopropenylvinyl ligands via insertion into a transient cyclopropenyl metal bond

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(8), P. 3629 - 3637

Published: Jan. 1, 2024

Tautomerism between rhodacyclobutadiene and σ-cyclopropenyl complexes is inferred to account for the facile insertion of alkynes afford unusually stable β-cyclopropenylvinyl complexes.

Language: Английский

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Asymmetric cyclization catalyzed by a chiral phosphoric acid–gold(I) hybrid complex as a multifunctional catalyst

Bulletin of the Chemical Society of Japan, Journal Year: 2024, Volume and Issue: 97(3)

Published: Feb. 29, 2024

Abstract We herein report the development of a novel hybrid complex containing gold(I) and chiral phosphoric acid moiety to generate multifunctional catalyst. While use as bifunctional catalyst is common strategy in asymmetric organic synthesis, acid–transition metal complexes catalysts have not been investigated. Thus, we designed synthesized that promotes catalytic reactions through multipoint nonclassical noncovalent interactions substrates lack classical hydrogen-bond donors. In addition, demonstrate its usefulness by successfully developing first synthesis dihydrocyclohepta[b]indoles. Experimental theoretical studies revealed this reaction involves kinetic resolution intermediate, favored diastereomeric transition state for yielding enantiomeric products formed originating from acid–base nature moiety.

Language: Английский

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A Study on Fabrication and Characterization of Alchemic Metal

International Journal For Multidisciplinary Research, Journal Year: 2024, Volume and Issue: 6(2)

Published: April 16, 2024

In this Research, The Preparation and characterization of gold(Ag) Particles by Biosynthesis process are carried out. synthesis gold Particles, Green Leafy vegetables salts like Saltpetre Ammonium Sulphate being used as a base agent to get down the proton in semi-synthesized particles. After Attraction synthesized particles formed Then Morphological Characteristics such UV-spectroscopy is observe formation particles, XRD analysis out study crystallinity, orientation shape, Size observed through SEM analysis. Finally, FTIR Measurements identify presence various chemical groups Gold Hence may be for different coating applications.

Language: Английский

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