A photocatalyzed formal (3+2) cycloaddition has been developed to construct original polysubstituted α-SCF cyclopentanones in a regio- and diastereoselective manner. This building block approach leverages trifluoromethylthio alkynes and branched/linear aldehydes, as readily available reaction partners, in consecutive hydrogen atom transfers and C-C bond formations. Difluoromethylthio alkynes are also compatible substrates. Furthermore, the potential for telescoped reaction starting from alcohols instead of aldehydes was demonstrated, as well as process automatization and scale-up under continuous microflow conditions. This prompted density functional theory (DFT) calculations to support a radical-mediated cascade process.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.202407689 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Inserted-B atoms modulating electronic structure of Pt enhancing hydrogen evolution under Universal-pH.
J Colloid Interface Sci
January 2025
College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108 China. Electronic address:
The development of high-performance electrocatalysts for hydrogen evolution reaction (HER) in different pH conditionsis pivotal in producing green hydrogen, but remains challenging. Herein, we regulate the p-d orbitals hybridization between B and Pt for effective and durable HER at all pH ranges by controlling the inserted B atom. Consequently, the optimized B-doped Pt catalysts with 20 at.
View Article and Find Full Text PDFElectrostatically tuning radical addition and atom abstraction reactions with distonic radical ions.
Chem Sci
January 2025
Molecular Horizons and School of Chemistry and Molecular Bioscience, University of Wollongong Wollongong New South Wales 2522 Australia
Although electrostatic catalysis can enhance the kinetics and selectivity of reactions to produce greener synthetic processes, the highly directional nature of electrostatic interactions has limited widespread application. In this study, the influence of oriented electric fields (OEF) on radical addition and atom abstraction reactions are systematically explored with ion-trap mass spectrometry using structurally diverse distonic radical ions that maintain spatially separated charge and radical moieties. When installed on rigid molecular scaffolds, charged functional groups lock the magnitude and orientation of the internal electric field with respect to the radical site, creating an OEF which tunes the reactivity across the set of gas-phase carbon-centred radical reactions.
View Article and Find Full Text PDFA DNA phosphorothioation pathway via adenylated intermediate modulates Tdp machinery.
Nat Chem Biol
January 2025
Department of Gastroenterology, Hubei Clinical Center and Key Laboratory of Intestinal and Colorectal Disease, TaiKang Center for Life and Medical Sciences, Zhongnan Hospital of Wuhan University, School of Pharmaceutical Sciences, Wuhan University, Wuhan, China.
In prokaryotes, the non-bridging oxygen in the DNA sugar-phosphate backbone can be enzymatically replaced by a sulfur atom, resulting in phosphorothioate (PT) modification. However, the mechanism underlying the oxygen-to-sulfur substitution remains enigmatic. In this study, we discovered a hypercompact DNA phosphorothioation system, TdpABC, in extreme thermophiles.
View Article and Find Full Text PDFIntegrated analysis of cellulose structure and properties using solid-state low-field H-NMR and photoacoustic spectroscopy.
Sci Rep
January 2025
Nonprofitable Organization Touche NPO, Sapporo, 060-004, Japan.
In this study, we explore the structural intricacies of cellulose, a polymer composed of glucose monomers arranged in a linear chain, primarily investigated through solid-state NMR techniques. Specifically, we employ low-field proton nuclear magnetic resonance (H-NMR) to delve into the diverse hydrogen atom types within the cellulose molecule. The low-field H-NMR technique allows us to discern these hydrogen atoms based on their distinct chemical shifts, providing valuable insights into the various functional groups present in cellulose.
View Article and Find Full Text PDFContinuous photo-oxidation of methane to methanol at an atomically tailored reticular gas-solid interface.
Nat Commun
January 2025
Research Center for Solar Driven Carbon Neutrality, School of Physics Science and Technology, In-stitute of Life Science and Green Development, Hebei University, Baoding, 071002, PR China.
Photo-oxidation of methane (CH) using hydrogen peroxide (HO) synthesized in situ from air and water under sunlight offers an attractive route for producing green methanol while storing intermittent solar energy. However, in commonly used aqueous-phase systems, photocatalysis efficiency is severely limited due to the ultralow availability of CH gas and HO intermediate at the flooded interface. Here, we report an atomically modified metal-organic framework (MOF) membrane nanoreactor that promotes direct CH photo-oxidation to methanol at the gas-solid interface in a reticular open framework.
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!