A type of metal-free organic photo-Fenton-like reaction was developed, which was realized by a combination of UV with benzoates and peroxides. The findings here not only provide a novel ˙OH production pathway, but also shed new light on the accurate quantification, better use or prevention of ˙OH in many scenarios.
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http://dx.doi.org/10.1039/d0cc02633f | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Texas A&M University, Chemistry, UNITED STATES OF AMERICA.
The functionalization of pyridines at positions remote to the N-atom remains an outstanding problem in organic synthesis. The inherent challenges associated with overriding the influence of the embedded N-atom within pyridines was overcome using n-butylsodium, which provided an avenue to deprotonate and functionalize the C4-position over traditionally observed addition products that are formed with organolithium bases. In this work, we show that freshly generated 4-sodiopyrdines could undergo transition metal free alkylation reactions directly with a variety of primary alkyl halides bearing diverse functional groups.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Dermatology, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University, Chengdu, China.
Unsymmetric disulfides are prevalent in natural products and are essential in medicinal chemistry and materials science, but their robust synthesis poses significant challenges. In this paper, we report an expeditous transition-metal-free methodology for synthesizing unsymmetric disulfides through the addition of perthiyl radicals to alkenes. This study marks the use of generating perthiyl radicals by reacting SO with unactivated alkyl (pseudo)halides (Cl/Br/I/OTs).
View Article and Find Full Text PDFNat Commun
December 2024
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing, 210037, China.
Carbon nanomaterials show outstanding promise as electrocatalysts for hydrogen peroxide (HO) synthesis via the two-electron oxygen reduction reaction. However, carbon-based electrocatalysts that are capable of generating HO at industrial-level current densities (>300 mA cm) with high selectivity and long-term stability remain to be discovered. Herein, few-layer boron nanosheets are in-situ introduced into a porous carbon matrix, creating a metal-free electrocatalyst (B-C) with HO production rates of industrial relevance in neutral or alkaline media.
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).
View Article and Find Full Text PDFAdv Mater
December 2024
College of Physics and Center of Quantum Materials and Devices, Chongqing University, Chongqing, 401331, China.
Achieving efficient and sustainable hydrogen production through photocatalysis is highly promising yet remains a significant challenge, especially when replacing costly noble metals with more abundant alternatives. Conversion efficiency with noble-metal-free alternatives is frequently limited by high charge recombination rates, mainly due to the sluggish transfer and inefficient consumption of photo-generated holes. To address these challenges, a rational design of noble-metal-free cocatalysts as oxidative sites is reported to facilitate hole consumption, leading to markedly increased H yield rates without relying on expensive noble metals.
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