The elusive reaction mechanism of Mn(ii)-mediated benzylic oxidation of alkylarene by H2O2: a gem-diol mechanism or a dual hydrogen abstraction mechanism? DOI
Shoujun Wang, Dongru Sun, Zhi Min Wu

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(48), P. 18247 - 18256

Published: Jan. 1, 2023

The gem -diol, dual-hydrogen abstraction (DHA), and reversed-DHA reaction pathways are involved in the alcohol oxidation of hydroxylated phenylbutanoic acid to form desired arene ketones.

Language: Английский

Yb-Doped CuY modulates Cu electronic structures for efficient oxidation of anisole to guaiacol DOI Creative Commons
Hanghang Zhang, Gang Xu

RSC Advances, Journal Year: 2025, Volume and Issue: 15(13), P. 9899 - 9909

Published: Jan. 1, 2025

Yb-Doped CuY catalysts enhance the electronic structure of copper for efficient hydrogen peroxide oxidation anisole to guaiacol, achieving improved conversion rates and selectivity.

Language: Английский

Citations

0
Discussing the Terms Biomimetic and Bioinspired within Bioinorganic Chemistry DOI Creative Commons
Silène Engbers, Phebe H. van Langevelde, Dennis G. H. Hetterscheid

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(43), P. 20057 - 20067

Published: Sept. 23, 2024

The terms biomimetic and bioinspired are very relevant in the field of bioinorganic chemistry have been widely applied. Although they were defined by International Organization for Standardization 2015, these at times used rather ambiguously literature. This may be due to inherent complexity systems where, example, a structural model an enzyme active site not replicate its function. Conversely, function reproduced system where structure does resemble enzyme's site. To address this, we suggest definitions wherein decoupled. With help some representative case studies outlined challenges that arise make suggestions on how apply terminology with careful intention.

Language: Английский

Citations

2
Cu-Promoted ipso-Hydroxylation of sp2 Bonds with Concomitant Aromatic 1,2-Rearrangement Involving a Cu-oxyl-hydroxo Species DOI Creative Commons

Sunipa Goswami,

Karan Gill,

Xinyi Yin

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(43), P. 20675 - 20688

Published: Oct. 18, 2024

Herein, we report the first example of Cu-promoted β ipso-hydroxylation substituted benzophenones using a bidentate directing group (DG) and H2O2 as an oxidant. In addition to new C–O bond formed, ipso-oxidation induces very unusual 1,2-rearrangement iminyl vicinal γ position. This transformation is highly dependent on substrate utilized (favored for 4-methoxy-substituted benzophenones) DG used (2-picolylamine leads selective γ-C–H functionalization, while requires 2-(2-aminoethyl)pyridine). An analysis oxidation substrate–ligands derived from 2-(2-aminoethyl)pyridine unsymmetrical 4-MeO-substituted indicates high regioselectivity (up 89:11 MeO-substituted arene ring up 92:8 ipso- vs hydroxylation). Mechanistic studies (which include spectroscopic characterization reaction intermediates, kinetics, calculations) suggest formation mononuclear CuIIOOH species before rate-determining step (rds) reaction. DFT calculations that hydroxylation pathway involves one-step concerted O–O cleavage electrophilic aromatic attack. Conversely, occurs in stepwise fashion, which produces CuIII(O·)(OH) Calculations also shed light mechanism step, strain release spiro 5-membered 6-membered Cu chelate.

Language: Английский

Citations

1
Photoredox/Iron Dual-Catalysis-Enabled [4 + 2] Cyclization of Acyl Nitrene with Alkynes DOI
Shimin Xie,

Shuwang Tang,

Ming Hou

et al.

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

Published: Dec. 13, 2024

In this work, the annulation of acyl nitrene with alkynes is reported under photoredox/iron dual-catalysis for synthesis a series isoquninalin-2-ones. The reaction featured high regioselectivity and good generality. particular, resulting isoquinalin-2-ones could be structurally elaborated into several biologically interesting scaffolds. Mechanism investigation suggests that was ascribed to formal [4 + 2] cyclization. It believed represents an initial example preparing isoquinolin-1-ones from ferric peroxyl-catalyzed insertion.

Language: Английский

Citations

1
Intramolecular C–H Oxidation in Iron(V)-oxo-carboxylato Species Relevant in the γ-Lactonization of Alkyl Carboxylic Acids DOI Creative Commons

Andrea Álvarez-Núñez,

Rudraditya Sarkar, Valeria Dantignana

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 14183 - 14194

Published: Sept. 11, 2024

High-valent oxoiron species have been invoked as oxidizing agents in a variety of iron-dependent oxygenases. Taking inspiration from nature, selected nonheme iron complexes developed catalysts to elicit C-H oxidation through the mediation putative oxoiron(V) species, akin those proposed for Rieske The addition carboxylic acids these iron-catalyzed oxidations has proved highly beneficial terms product yields and selectivities, suggesting direct involvement iron(V)-oxo-carboxylato species. When acid functionality is present alkane substrate, it acts directing group, enabling selective intramolecular γ-C-H hydroxylation that eventually affords γ-lactones. While this mechanistic frame solidly supported by previous studies, spectroscopic detection key intermediate its competence engaging leading lactonization not accomplished. In work, we generate series well-defined (

Language: Английский

Citations

0
The elusive reaction mechanism of Mn(ii)-mediated benzylic oxidation of alkylarene by H2O2: a gem-diol mechanism or a dual hydrogen abstraction mechanism? DOI
Shoujun Wang, Dongru Sun, Zhi Min Wu

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(48), P. 18247 - 18256

Published: Jan. 1, 2023

The gem -diol, dual-hydrogen abstraction (DHA), and reversed-DHA reaction pathways are involved in the alcohol oxidation of hydroxylated phenylbutanoic acid to form desired arene ketones.

Language: Английский

Citations

0