The application of acyl radicals in radical addition reactions in the absence of a CO atmosphere is generally limited to aryl or alpha-unsubstituted alkyl acyl radicals due to competing decarbonylations where the rate constant for this degradation process surpasses 104 s-1. In this work, a potential solution to avoid the problem of decarbonylations is presented employing N-acyl oxazolidinones which are reduced to acyl radical equivalents in the presence of samarium diiodide and water. In the company of an acrylamide, acrylate, or acrylonitrile, the product from a formal acyl radical addition is obtained in yields up to 87%. Examples are given where the decarbonylation rate constants even exceed 108 s-1. It is proposed that the reaction proceeds via a ketyl-like intermediate.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja050420u | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Stereoselective amino alcohol synthesis via chemoselective electrocatalytic radical cross-couplings.
Nat Chem
January 2025
Department of Chemistry, Scripps Research, La Jolla, CA, USA.
Amino alcohols are vital in natural products, pharmaceuticals and agrochemicals, and as key building blocks for various applications. Traditional synthesis methods often rely on polar bond retrosynthetic analysis, requiring extensive protecting group manipulations that complicate direct access. Here we show a streamlined approach using a serine-derived chiral carboxylic acid in stereoselective electrocatalytic decarboxylative transformations, enabling efficient access to enantiopure amino alcohols.
View Article and Find Full Text PDFChemical Composition, Free Radicals and Pathogenic Microbes in the Extract Derived from : In Silico and In Vitro Approaches.
Mar Drugs
December 2024
Plant Biotechnology Team, Faculty of Sciences, Abdelmalek Essaadi University, Tetouan 93002, Morocco.
Marine algae are renowned for their health benefits due to the presence of functional bioactive compounds. In this context, this study aims to valorize the extract of a seaweed, (), through phytochemical characterization using liquid chromatography-mass spectrometry (HPLC-MS), as well as in vitro and in silico evaluation of its biological activities (antioxidant and antimicrobial). Phytochemical characterization revealed that the ethanolic extract of (DdEx) is rich in phenolic compounds, with a total of 22 phycocompounds identified.
View Article and Find Full Text PDFC(sp2)-H Acylation of benzo[h]quinolines at Room Temperature via Aldehyde Autoxidation and Palladium Catalysis Cooperation.
Chemistry
December 2024
Indian Association for the Cultivation of Science, School of Chemical Sciences, 2A & 2B Raja S. C. Mullick Road, Jadavpur, 700032, Kolkata, INDIA.
Herein, we report Pd-catalyzed C(sp2)-H acylation using aldehyde as acyl source and O2 as the green oxidant at room temperature. A selective association of acyl radical formed in-situ during aldehyde autoxidation with Pd-catalysis is the key to the process. The reaction afforded products in good yields (up to 82%) and it is scalable.
View Article and Find Full Text PDFTunable Thiazolium Carbenes for Enantioselective Radical Three-Component Dicarbofunctionalizations.
J Am Chem Soc
December 2024
Laboratory of Asymmetric Catalysis and Synthesis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Asymmetric -heterocyclic carbene (NHC) organocatalysis is a cornerstone of synthetic organic chemistry. The emerging concept of single-electron NHC catalysis broadened the scope of C-C bond-forming reactions, facilitating the synthesis of a variety of attractive racemic compounds. However, the development of effective and selective chiral NHC catalysts for asymmetric radical-mediated reactions has been challenging.
View Article and Find Full Text PDFQuercetin inhibits hydrogen peroxide-induced cleavage of heat shock protein 90 to prevent glutathione peroxidase 4 degradation via chaperone-mediated autophagy.
Phytomedicine
November 2024
School of Pharmacy, Hunan University of Chinese Medicine, Changsha 410208, China; Center for standardization and functional engineering of traditional Chinese medicine in Hunan province, Changsha 410208, China; Key Laboratory of Modern Research of TCM, Education Department of Hunan Province, Changsha 410208, China. Electronic address:
Background: Oxidative stress is caused by the accumulation of reactive oxygen species (ROS) and the depletion of free radical scavengers, which is closely related to ferroptosis in diseases. Quercetin, as a natural flavonoid compound, has been reported to have multiple pharmacological effects on the basis of its anti-oxidative and anti-ferroptotic activities. This study was designed to explore the specific mechanism of quercetin against ferroptosis induced by hydrogen peroxide (HO).
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!