Zirconacyclopropenylboronates can be stabilized to dimerization by complexation with tributylphosphine; the phosphine stabilized zirconacycle boronates react with aliphatic and aromatic ketones and aldehydes at C2 of the triple bond to give the previously unknown 3-hydroxyvinylboronates in 61-80% isolated yields.
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http://dx.doi.org/10.1039/b811287h | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland.
Organic redox systems that can undergo oxidative and reductive (ambipolar) electron transfer are elusive yet attractive for applications across synthetic chemistry and energy science. Specifically, the use of ambipolar redox systems in proton-coupled electron transfer (PCET) reactions is largely unexplored but could enable "switchable" reactivity wherein the uptake and release of hydrogen atoms are controlled using a redox stimulus. Here, we describe the synthesis and characterization of an ambipolar functionalized terthiophene (TTH) bearing methyl thioether and phosphine oxide groups that exhibits switchable PCET reactivity.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
TU Dortmund: Technische Universitat Dortmund, Fakultät für Chemie und Chemische Biologie, Otto-Hahn Str.6, 44227, Dortmund, GERMANY.
This study introduces a novel class of carbon-centered diradicals: a monosubstituted C-atom stabilized by a phosphine. The diradical Ph3P→C was photochemically generated from a diazophosphorus ylide precursor (Ph3PCN2) and characterized by EPR and isotope-sensitive ENDOR spectroscopy at low temperatures. Ph3P→C features an axial zero-field splitting parameter D = 0.
View Article and Find Full Text PDFACS Omega
January 2025
Department of Chemistry and Biochemistry, University of Colorado Colorado Springs, 1420 Austin Bluffs Parkway, Colorado Springs, Colorado 80918 United States.
The development of a sensitive and selective silver nanoparticle assay for the quantitation of vitamin C (SNaP-C), as ascorbic acid (AA) and total ascorbic acid (TAA = AA + dehydroascorbic acid, DHAA), is described. Three assay parameters were investigated and optimized: (1) synthesis of silver nanoparticles (AgNPs) to produce a reliable enhanced localized surface plasmon resonance (LSPR) in the presence of specific added antioxidants; (2) ensuring long-term stability of AA and DHAA in aqueous solutions; and (3) SNaP-C assay conditions to allow for rapid analysis of samples (beverages) by monitoring the enhanced LSPR. The synthesis of AgNPs using soluble starch as a capping agent and d-arabinose as a reducing agent was optimized in a CEM Discover SP laboratory microwave.
View Article and Find Full Text PDFJ Org Chem
January 2025
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, 2025 Chengluo Avenue, Chengdu 610016, P.R. China.
Herein, we report the first example that P(O)-H species including -phosphonates and -phosphine oxides could participate in a highly regioselective 1,4-addition to in situ generated 1-benzopyrylium ion from C3-substituted 2-chromene hemiketals, which provides a brand-new and effective approach for the synthesis of C4-phosphorylated 4-chromenes with diverse C3-functionality (ketone, ester, sulfonyl, aryl, and alkyl groups). In total, the reaction features the use of inexpensive Zn(ClO)·6HO as a catalyst, low catalyst loading (only 5 mol %), mild reaction conditions (60 °C, 10 min to 24 h), and broad substrate scope (46 examples) as well as good to high yields (>90% yield on average). More importantly, mechanistic experiments demonstrated the essential role of the C3-substituent on 2-chromene hemiketals in stabilizing the in situ generated 1-benzopyrylium ion and the regioselective 1,4-addition control.
View Article and Find Full Text PDFNanoscale
January 2025
Institue of Materials Chemistry, TU Wien, Getreidemarkt 9/E165, 1060 Vienna, Austria.
In the field of nanocluster catalysis, it is crucial to understand the interplay of different parameters, such as ligands, support and pretreatment and their effect on the catalytic process. In this study, we chose the selective hydrogenation of phenylacetylene as a model reaction and employed two gold nanoclusters as catalysts, the phosphine protected Au and the thiolate protected Au, each with different binding motifs. They were supported on MgO, AlO and a hydrotalcite (HT), chosen for their different acidity.
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