Reported herein is a visible-light-catalyzed photoredox atom-transfer radical cyclization (ATRC) halo-alkylation of 1,6-dienes with α-halo-ketones as the ATRC reagent. This process exhibits high atom economy, high step economy, and high redox economy, which can directly construct a 4-bromo-3,3-dialkyl-octahydro-indol-2-one core under mild conditions in one pot, and lutidine is found to be the key promoter for this ATRC process.
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http://dx.doi.org/10.1039/c9cc09876c | DOI Listing |
J Org Chem
January 2025
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
We herein disclose a visible-light-induced synthesis of aryl esters through the cross-dehydrogenative coupling of aldehydes with phenols using BrCCl, in which phenolate functions as both a substrate and a photosensitizer. This transition-metal- and photocatalyst-free visible-light-induced esterification is suitable for a wide range of substrates and gives moderate to excellent yields (up to 95%). Mechanistic studies provided evidence of a self-propagating radical reaction involving homolytic cleavage of the aldehydic C-H bond and the formation of acyl bromides.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
In traditional atom transfer radical polymerization (ATRP), oxygen must be meticulously eliminated due to its propensity to quench radical species and halt the polymerization process. Additionally, oxygen oxidizes the lower-valent Cu catalyst, compromising its ability to activate alkyl halides and propagate polymerization. In this study, we present an oxygen-driven ATRP utilizing alkylborane compounds, a method that not only circumvents the need for stringent oxygen removal but also exploits oxygen as an essential cofactor to promote polymerization.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
The synthesis of polymers with well-defined composition, architecture, and functionality has long been a focal area of research in the field of polymer chemistry. The advancement of controlled radical polymerization (CRP) has facilitated the synthesis of precise polymers, which are endowed with new properties and functionalities, thereby exhibiting a wide range of applications. However, radical polymerization faces several challenges, such as oxygen intolerance, and common thermal initiation methods may lead to side reactions and depolymerization.
View Article and Find Full Text PDFDiscov Nano
January 2025
Institute of Science, Department of Chemistry, Firat University, 23200, Elazığ, Turkey.
In this study, firstly chitin was reacted with chloracetyl chloride to synthesize the macroinitiator chitinchloroacetate (Ch.ClAc). Then, graft copolymers of methacrylamide (MAM), diacetone acrylamide (DAAM), N-(4-nitrophenyl)acrylamide (NPA), and 2-hydroxyethyl methacrylate (HEMA) monomers were synthesized by atom transfer radical polymerization (ATRP).
View Article and Find Full Text PDFPLoS One
January 2025
Chemistry and Biochemistry, University of St. Thomas, Houston, TX, United States of America.
Cardiovascular disease (CVD) remains the leading cause of morbidity and mortality globally, with oxidative stress playing a pivotal role in its progression. Free radicals produced via oxidative stress contribute to lipid peroxidation, leading to subsequent inflammatory responses, which then result in atherosclerosis. Antioxidants inhibit these harmful effects through their reducing ability, thereby preventing oxidative damage.
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