Alkoxy radicals are versatile reactive intermediates in organic synthesis. Here, we leverage the principle of frustrated radical pair to provide convenient access to these highly reactive species directly from tertiary alcohols via oxoammonium-mediated oxidation of the corresponding alkoxides. This approach enabled various synthetically useful transformations including β-scission, radical cyclization, and remote C-H functionalization, giving rise to versatile alkoxyamines that can be further elaborated to various functionalities.
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http://dx.doi.org/10.1021/jacs.4c07125 | DOI Listing |
Nat Commun
January 2025
School of Materials Science and Chemical Engineering, Institute of Drug Discovery Technology, Institute of Mass Spectrometry, Zhejiang Engineering Research Center of Advanced Mass Spectrometry and Clinical Application, Ningbo University, Ningbo, PR China.
C-C bond cleavage and recombination provide an efficient strategy for the modification and reconstruction of molecule structures. Herein, we present a method for achieving amidation of aryl C(sp)-H bond through the cleavage and recombination of C-C triple bond with the involvement of nitrous acid esters. This method marks the instance of precise and controlled stepwise cleavage of C-C triple bond, offering a fresh perspective for the cleavage of such bonds.
View Article and Find Full Text PDFMater Horiz
January 2025
College of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou, Henan 450002, China.
A new photopolymerizable organic-inorganic (O-I) hybrid sol-gel material, AUP@SiO-184, has been synthesized and utilized as a gate dielectric in flexible organic thin-film transistors (OTFTs). The previously reported three-arm alkoxy-functionalized silane amphiphilic polymer has yielded stable O-I hybrid materials comprising uniformly dispersed nanoparticles in the sol state. In this study, a photosensitizer was introduced, facilitating curing effects under ultraviolet light.
View Article and Find Full Text PDFEnviron Sci Technol
January 2025
School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Fenton-like reactions between organic peroxides and transition-metal ions in the atmospheric aqueous phase have profound impacts on the chemistry, composition, and health effects of aerosols. However, the kinetics, mechanisms, and key influencing factors of such reactions remain poorly understood. In this study, we synthesized a series of monoterpene-derived α-acyloxyalkyl hydroperoxides (AAHPs), an important class of organic peroxides formed from Criegee intermediates during the ozonolysis of alkenes, and investigated their Fenton-like reactions with iron ions in the aqueous phase.
View Article and Find Full Text PDFTalanta
January 2025
Dipartimento di Chimica e Biologia "A. Zambelli", Università degli Studi di Salerno, Via Giovanni Paolo II 132, 84084, Fisciano, (SA), Italy.
Despite intense investigation on the subject, the information available on the antioxidant capacity of natural coumarins and furanocoumarins is controversial. In the present study the antioxidant capacity of 19 pure naturally occurring compounds, among which 5 coumarins and 14 furanocoumarins is determined, using both the coulometrically determined antioxidant capacity (CDAC) and linear sweep voltammetry (LSV). None of the coumarins and furanocoumarins assayed exhibited appreciable scavenging activity against the DPPH radical.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Chemistry, University of Helsinki, Helsinki, Finland.
Secondary organic aerosols (SOAs) significantly impact Earth's climate and human health. Although the oxidation of volatile organic compounds (VOCs) has been recognized as the major contributor to the atmospheric SOA budget, the mechanisms by which this process produces SOA-forming highly oxygenated organic molecules (HOMs) remain unclear. A major challenge is navigating the complex chemical landscape of these transformations, which traditional hypothesis-driven methods fail to thoroughly investigate.
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