Divergent Reactivity of <i>E</i>/<i>Z</i>‐Azobenzene‐Based Phosphine‐Gold Catalysts: Toward an ON‐ON Catalytic Photoswitch Process DOI Creative Commons

Nawel Goual,

Stéphane Maisonneuve, Fabrizio Medici

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 367(1)

Published: Oct. 17, 2024

Abstract This work discloses a strategy for the implementation of ON‐ON organometallic catalytic processes using photoresponsive phosphine ligands. The approach leverages on regiodivergent reactivity mono‐ and bimetallic gold complexes that results from π‐ vs σ,π‐activations alkynyl‐substituted urea substrates, selective formation either dihydroquinazolinone or indole‐carboxamide products, via intramolecular hydroamidation.

Language: Английский

Tailoring the Coordination Environment of Cu Single Atoms for Achieving Regioselective C–C Bond Activation of Amides DOI

Wunengerile Zhang,

Chaolumen Bai,

Dan Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 18408 - 18418

Published: Dec. 2, 2024

C–C bond activation can provide a direct reconstruction strategy of carbon skeletons to furnish number structurally diverse molecules. In general, regioselectivity represents the state-of-the-art owing existence several different carbon–carbon bonds, having high BDE, ∼90 kcal/mol. Here, we report directed for amides concise synthesis range urea derivatives and carbamates via regioselective enabled by heterogeneous single-atom copper catalyst (Cu-SAC), with turnover frequency 249 h–1, which is 19 times higher than that analogous homogeneous catalyst. Multitechnique characterization data show Cu species are associated an unsaturated coordination structure plentiful oxygen vacancies on γ-Al2O3 facilitate adsorption multiple coordinated dioxygen, leading catalytic activity selectivity. It would offer opportunities speed up heterogenized process catalysts in inert-bond reactions.

Language: Английский

Citations

4
Subcellular Photocatalysis Enables Tumor-Targeted Inhibition of Thioredoxin Reductase I by Organogold(I) Complexes DOI

Moyi Liu,

Hai‐Tao Liu, Yanlian Yang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Selective inhibition of TrxR1 over TrxR2 is a highly sought-after goal, because the two enzymes play distinct roles in cancer progression. However, achieving targeted challenging due to their high homology and identical active site sequence. Herein we report new subcellular photocatalysis approach for by controllably activating organogold(I) prodrugs within cytosol, exclusive location TrxR1. The NHC-Au(I)-alkynyl complexes are stable evenly distributed cell; they can meanwhile be efficiently transformed into NHC-Au(I)-L species (L = labile ligands) via radical mechanism photocatalysts released cytosol (from endosome/lysosome) upon light irradiation, leading selective without affecting TrxR2. This results strong cytotoxicity cells with much higher selectivity than auranofin, pan TrxR inhibitor that cannot discriminate TrxR1/2, along potent antitumor activities multiple zebrafish mouse models. prodrug activation may thus suggest novel precision targeting using remarkable spatial control photocatalysis.

Language: Английский

Citations

0
Trinuclear gold-catalyzed site-selective alkylation of peptides DOI

Qing-Yun Fang,

Chengyihan Gu,

Yinghan Chen

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 14, 2024

Language: Английский

Citations

2
Unlocking the Aromatic Cope Rearrangement with Gold(I) Catalysis DOI

Pierre Locquet,

R. Akilan,

Raquel Pereira

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 18884 - 18895

Published: Dec. 12, 2024

Language: Английский

Citations

1
Control over Anion Coordination on Pd(II), Cu(I), and Ag(I) with Regioisomeric Phosphine‐Carboxylate Ligands DOI Creative Commons
Elisa González‐Fernández, Nittert Marinus, Jyoti Dhankhar

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(37)

Published: May 1, 2024

Abstract The coordination of anionic donors is involved at various stages catalytic cycles in transition‐metal catalysis, but control over the spatial positioning anions around a metal center challenge chemistry. Here we show that regioisomeric phosphine‐carboxylate ligands provide anion on palladium(II) centers by favoring either κ 2 , cis ‐κ 1 or trans carboxylate donor. Additionally, carboxylates, which contain methyl donor, upon protonation, deliver metal‐alkyl complexes feature coordinated carboxylic acid. Such can be considered as models for minima follow concerted metalation‐deprotonation transition state C−H activation. predictability modes further demonstrated silver(I) and copper(I) centers, less common structures mononuclear dinuclear obtained using control. Our results demonstrate potential

Language: Английский

Citations

0
Theoretical study of Ni(0)-catalyzed intermolecular hydroamination of branched 1,3-dienes: reaction mechanism, regioselectivity, enantioselectivity, and prediction of the ligand DOI
Fen Wang, Changbao Chen, Feng Zhang

et al.

Journal of Molecular Modeling, Journal Year: 2024, Volume and Issue: 31(1)

Published: Dec. 11, 2024

Language: Английский

Citations

0
Ag/Au-Catalyzed Functionalization of Heterocycles Through C–H Activation DOI
Nurullah Saraçoğlu

Topics in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Language: Английский

Citations

0
Divergent Reactivity of <i>E</i>/<i>Z</i>‐Azobenzene‐Based Phosphine‐Gold Catalysts: Toward an ON‐ON Catalytic Photoswitch Process DOI Creative Commons

Nawel Goual,

Stéphane Maisonneuve, Fabrizio Medici

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 367(1)

Published: Oct. 17, 2024

Abstract This work discloses a strategy for the implementation of ON‐ON organometallic catalytic processes using photoresponsive phosphine ligands. The approach leverages on regiodivergent reactivity mono‐ and bimetallic gold complexes that results from π‐ vs σ,π‐activations alkynyl‐substituted urea substrates, selective formation either dihydroquinazolinone or indole‐carboxamide products, via intramolecular hydroamidation.

Language: Английский

Citations

0