Using Eosin Y as a metal-free photocatalyst and O as an oxidant, the present study reports a new photochemical protocol that enables efficient aerobic oxidation of various benzyl alcohols to the corresponding aldehydes or ketones in excellent yields under mild reaction conditions. The catalyst system presents good functional-group tolerance and exquisite chemoselectivity, which also can easily be scaled-up to gram scale. Moreover, the methodological applications in practical synthesis of several organic molecules and the primary reaction mechanism were also discussed.
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http://dx.doi.org/10.1021/acs.joc.2c02667 | DOI Listing |
Dalton Trans
January 2025
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Phosphole and azaphosphole derivatives with triazole functionalities, [CH{1,2,3-NCCHC(PPh)}] (L1) and [CH{1,2,3-NC(Ph)C(PPh)}] (L2) were synthesized by reacting [(CH)(1,2,3-NC = CH--Br-CH)] and [(-Br-CH)(1,2,3-NC = CHCH)] with BuLi followed by the addition of dichlorophenylphosphine. The reactions of L1 and L2 with an excess of 30% HO afforded phosphole oxides [CH{1,2,3-NCCHC(P(O)Ph)}] (L1O) and [CH{1,2,3-NC(Ph)C(P(O)Ph)}] (L2O) as white crystalline solids. Stoichiometric reactions of L1 and L2 with [Ru(η--cymene)Cl] in CHCl yielded [RuCl(η--cymene)(L1-κ-)] (1) and [RuCl(η--cymene)(L2-κ-)] (2), respectively.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Griffith University, Griffith School of Environment, Centre for Clean Environment and Energy, 4222, Brisbane, AUSTRALIA.
Converting biomass-derived molecules like 5-hydroxymethylfurfural (HMF) into value-added products alongside hydrogen production using renewable energy offers significant opportunities for sustainable chemical and energy production. Yet, HMF electrooxidation requires strong alkaline conditions and membranes for efficient conversion. These harsh conditions destabilize HMF, leading to humin formation and reduced product purity, meanwhile membranes increase costs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Nanjing University of Science and Technology, nanoscience and nanotechnology, Xiaolin wei 200, 210094, Nanjing, CHINA.
Suppressing over-oxidation is a crucial challenge for various chemical intermediate synthesis in heterogeneous catalysis. The distribution of oxidative species and the substrate coverage, governed by the direction of electron transfer, are believed to influence the oxidation extent. In this study, we present an experimental realization of surface coverage modulation on a photoelectrode using a photo-induced charge activation method.
View Article and Find Full Text PDFChemistry
December 2024
Technische Universitat Berlin, Chemistry, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, GERMANY.
Water-assisted electrocatalytic oxidation of alcohols into valuable chemicals is a promising strategy to circumvent the sluggish kinetics of water oxidation, while also reducing cell voltage and improving energy efficiency. Recently, transition metal (TM)-based catalysts have been investigated for anodic alcohol oxidation, but success has been limited due to competition from the oxygen evolution reaction (OER) within the working regime. In this study, NiCo-based Prussian blue analog (PBA) was electrochemically activated at the anodic potential to produce a Co-Ni(O)OH active catalyst with a nanosheet-like architecture.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, New Cornerstone Science Laboratory, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China.
Reported herein is the generation of -quinone methides (-QMs) via metal-free visible-light-induced oxidation of -alkylarenols, as well as their subsequent reaction with olefins to afford chromans in good to excellent yields (up to 91%). The key is the selective activation of the benzylic C(sp)-H bond of -alkylarenols via single electron transfer (SET) and the formation of -QMs via hydrogen atom transfer (HAT).
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