Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds DOI Creative Commons
Francesco Calogero,

Leonie Wilczek,

Emanuele Pinosa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 30, 2024

Abstract Excited states of radical anions derived from the photoreduction stable organic molecules are suggested to serve as potent reductants. However, excited these species too short‐lived allow bimolecular quenching processes. Recently, singlet state Meisenheimer complexes, which possess a long‐lived state, was identified competent for reduction challenging substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably and simply accessible different addition n BuLi readily available aromatic heterocycles investigated, photoreactivity generated studied. In this paper, we present straightforward preparation family powerful photoreductants (*E ox < −3 SCE in their states, determined by DFT time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation electron‐rich aryl chlorides form C−C bond through cyclization. Photophysical analyses computational studies combination with experimental mechanistic investigations demonstrate ability adduct act strong electron donor under visible light irradiation.

Language: Английский

Heterogeneous Mn@CeO2 Catalyst for α-Alkylation of Ketones with Alcohols via Hydrogen-Borrowing Strategy DOI Creative Commons

Rajagopal Swaathy,

S. Karthikeyan

ACS Omega, Journal Year: 2025, Volume and Issue: 10(9), P. 9649 - 9660

Published: Feb. 24, 2025

Construction of a C-C bond via alkylation ketones with alcohol as the alkylating source by employing hydrogen-borrowing strategy is attracting significant attention and highly appealing due to its simplicity, cost-effectiveness, environmental benefits, fact that water only byproduct. The development heterogeneous catalysts based on nonprecious base metals progressing rapidly. Our newly disclosed manganese-doped cerium oxide nanocomposite (10 wt % Mn@CeO2) stands out cost-efficient air-stable catalyst, synthesized through straightforward coprecipitation method employed for α-alkylation primary alcohols strategy. X-ray diffraction (XRD) analysis confirms high crystallinity CeO2, while field emission scanning electron microscopy (FE-SEM) high-resolution transmission (HR-TEM) images reveal MnO2 nanoparticles, measuring 19 nm in size, uniformly decorated rod-shaped CeO2 which have size 33 nm. photoelectron spectroscopy (XPS) uncovers presence Mn4+ species embedded nanorods. Electron paramagnetic resonance (EPR) further indicates surface defects contribute impressive catalytic yield, ranges from 70 98% α-alkylated ketones. Thermogravimetric (TGA) demonstrates remarkable thermal stability maintaining up 800 °C. Additionally, inductively coupled plasma mass spectrometry (ICP-MS) no leaching Mn ions, emphasizing heterogeneity catalyst. Remarkably, 10 Mn@CeO2 recycled six cycles loss activity. This study underscores synergistic effect between metal redox pair key exceptional activity reactions, making promising catalyst sustainable efficient formation.

Language: Английский

Citations

0
Design, synthesis and activity evaluation of benzene sulfonamide derivatives as novel androgen receptor antagonist DOI

Cong Bian,

Tianqi Wang, Meng Wu

et al.

European Journal of Medicinal Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 117712 - 117712

Published: May 1, 2025

Language: Английский

Citations

0
Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds DOI Creative Commons
Francesco Calogero,

Leonie Wilczek,

Emanuele Pinosa

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 30, 2024

Abstract Excited states of radical anions derived from the photoreduction stable organic molecules are suggested to serve as potent reductants. However, excited these species too short‐lived allow bimolecular quenching processes. Recently, singlet state Meisenheimer complexes, which possess a long‐lived state, was identified competent for reduction challenging substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably and simply accessible different addition n BuLi readily available aromatic heterocycles investigated, photoreactivity generated studied. In this paper, we present straightforward preparation family powerful photoreductants (*E ox < −3 SCE in their states, determined by DFT time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation electron‐rich aryl chlorides form C−C bond through cyclization. Photophysical analyses computational studies combination with experimental mechanistic investigations demonstrate ability adduct act strong electron donor under visible light irradiation.

Language: Английский

Citations

2
N-alkylation of amines with alcohols over hydrothermally prepared Nb-W mixed oxides DOI

Anas Abdullahi,

Kazu Okumura

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 570, P. 114669 - 114669

Published: Nov. 19, 2024

Language: Английский

Citations

1
A general catalyst for the base-free mono-N-alkylation of aromatic and aliphatic amines with alcohols DOI Creative Commons
Aitor Bermejo‐López, Man Li,

Naga Venkata Ranga Aditya Dharanipragada

et al.

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: 5(6), P. 101991 - 101991

Published: May 20, 2024

The catalytic alkylation of amines with alcohols is a highly atom-economical approach that produces water as the sole by-product. Existing systems lack generality and are primarily applicable to electron-poor or non-oxidizable amines, such anilines. outstanding effectiveness an Ir-NHC catalyst in forming C−N bonds from both aliphatic aromatic, presented here. performs remarkably under mild conditions, even at room temperature, attaining complete selectivity all tested cases toward monoalkylation, for challenging base-free conditions. Thorough mechanistic investigation understand activity selectivity, combining experimental, theoretical, situ ex X-ray absorption spectroscopy (XAS) studies, presented.

Language: Английский

Citations

0
Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds DOI Creative Commons
Francesco Calogero,

Leonie Wilczek,

Emanuele Pinosa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 30, 2024

Abstract Excited states of radical anions derived from the photoreduction stable organic molecules are suggested to serve as potent reductants. However, excited these species too short‐lived allow bimolecular quenching processes. Recently, singlet state Meisenheimer complexes, which possess a long‐lived state, was identified competent for reduction challenging substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably and simply accessible different addition n BuLi readily available aromatic heterocycles investigated, photoreactivity generated studied. In this paper, we present straightforward preparation family powerful photoreductants (*E ox < −3 SCE in their states, determined by DFT time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation electron‐rich aryl chlorides form C−C bond through cyclization. Photophysical analyses computational studies combination with experimental mechanistic investigations demonstrate ability adduct act strong electron donor under visible light irradiation.

Language: Английский

Citations

0