98%
921
2 minutes
20
A silicon-assisted C-O bond fragmentation strategy is developed by employing photoredox catalysis. This method describes an efficient transformative alternative for the dealkylation of aryl alkyl ethers comprising bioactive moieties. The protocol was successfully applied to the disintegration of lignin models and to the synthesis of an FLAP inhibitor. Detailed mechanistic investigations, with the help of computational studies, reveal the origin of the chemoselectivity and exclude the probability of unwanted parallel reactions.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.5c02502 | DOI Listing |
Chem Sci
August 2025
Department of Chemistry, University of Houston Houston Texas 77204 USA
Quantum mechanical tunnelling significantly influences the reactivity of strained ring systems, yet strategies for controlling such reactivity remain largely unexplored. Here, we identify geminal hyperconjugation, , electron delocalization between σ-bonds attached to a common atom, as a decisive electronic factor in governing heavy-atom tunnelling reactions involving three-membered rings. We illustrate this through a case study of the oxepin (1') ⇌ benzene oxide (1) equilibrium, recently shown to undergo solvent-controlled tunnelling at 3 K (, 2020, , 20318).
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
September 2025
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany.
In the structure of the title compound, CHN·CHNOS·CHNOS, the central pyridinic rings are approximately coplanar to the benzo-thia-zole moieties. The phenyl groups are appreciably angled to the central rings [inter-planar angles of 57.30 (3)° for the anion and 79.
View Article and Find Full Text PDFJ Phys Chem A
September 2025
School of Environmental Engineering, Henan University of Technology, Zhengzhou, Henan 450001, China.
Hydroxymethyl-methyl-α-lactone (HMML) is a key epoxide precursor in forming tracer compounds 2-methylglyceric acid (2-MG) or 2-methylglyceric acid sulfate (2-MGOS) from isoprene under high-NOx conditions. Despite its importance, the formation and transformation of HMML─particularly under acidic aerosol conditions─are still poorly understood, limiting comprehensive knowledge of secondary organic aerosol (SOA) formation. In this study, quantum chemical calculations, Born-Oppenheimer molecular dynamics (BOMD), and metadynamics (MTD) simulations are employed to investigate both the formation of HMML from methacryloyl peroxynitrate (MPAN) and its interfacial transformation mechanisms on sulfuric acid aerosols.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
Albomycins are unusual sulfur-containing nucleosides from the species of that exhibit potent antibiotic activities against both Gram-negative and Gram-positive bacteria including clinical pathogens. Previous studies demonstrated that the twitch radical SAM enzyme AbmM catalyzes an oxidative sulfur-for-oxygen swapping reaction converting CDP to a 4'-hydroxy-4'-thiocytidine 5'-diphosphate intermediate in the initial step of albomycin biosynthesis. However, the fate of this intermediate in the biosynthetic pathway has remained elusive.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Ethylene glycol (EG) derived from biomass and plastic wastes can serve as a sustainable H resource through steam reforming (HOCHCHOH + 2HO ⇄ 5H + 2CO). However, achieving high activity in H production with good selectivity toward CO under mild conditions poses a challenge. A thoughtful understanding of the active sites that accelerate the cleavage of the C-C bond rather than the C-O bond and the activation of the water molecule is still lacking.
View Article and Find Full Text PDF