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Achieving sustainable catalytic transformations requires synergistic optimization of solvent systems, catalytic motifs and energy inputs. Herein, we report a synergistic Pd/hydroquinone catalytic system that enables aerobic allylic C-H functions under ambient conditions (room temperature to 50°C, air) with high turnover frequency (TOF), using ethanol/water as a green medium. This strategy achieves unparalleled synthetic efficiency and demonstrates remarkable versatility across two pivotal transformations (alkylation and amination) involving over 90 products (up to 96% yield). It also delivers exceptional stereocontrol (up to 93% for quaternary stereocenters) and enables advanced allylic transformations within a green framework through additional synergistic catalysis. By integrating solvent engineering with cooperative catalysis, we have developed a scalable platform for the synthesis of allylic functionalized molecules with pharmaceutical interests, demonstrating how molecule-level innovation can drive sustainable industrial transformation.
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http://dx.doi.org/10.1093/nsr/nwaf196 | DOI Listing |
Inorg Chem
September 2025
Boston University, Chemistry Department, 590 Commonwealth Avenue, Boston, Massachusetts 02215, United States.
Previously published (NMe)[V(O)(μ-O)(pin)], has been shown to aerobically catalyze the oxidation of benzylic and allylic alcohols under mild conditions. Herein, we report syntheses of [V(O)(μ-O)(pin)] trimers, which are also active in OAD catalysis. Trimer formation requires an ammonium cation with at least two hydrogen atoms per cation (e.
View Article and Find Full Text PDFChem Biodivers
August 2025
Institute of Food Chemistry and Food Biotechnology, Justus Liebig University Giessen, Giessen, Germany.
The biocatalytic aerobic production of (E)-2-allylic aldehydes from their corresponding alcohols using lyophilisates of the basidiomycetous fungus Bjerkandera adusta is reported. The addition of small amounts of organic solvents to the reaction media increased the reaction and substrate conversion rates, allowing for to produce (E)-aldehydes under sustainable conditions. Citral (mixture of (E)- and (Z)-3,7-dimethylocta-2,6-dienal) was found as a result of the oxidation of geraniol ((E)-3,7-dimethyl-2,6-octadien-1-ol) as well as of nerol ((Z)-3,7-dimethyl-2,6-octadien-1-ol).
View Article and Find Full Text PDFSci Rep
August 2025
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Prof. Yousef Sobouti Boulevard, Zanjan, 45137-66731, Iran.
In this study, we describe the production of a novel high loading magnetic ionic nanoparticle network (HMINN) encompassing a functionalized imidazolium structure bridging between the core-shell magnetic nanoparticles. The network was constructed through the in situ radical polymerization of tris-vinyl imidazolium moieties on the surface of mercaptopropyl functionalized silica-coated magnetite. The structural and chemical features of the resulting material were comprehensively characterized utilizing various analytical methods such as N adsorption-desorption, FTIR, TGA, HRTEM, ICP, XPS, VSM and elemental analysis.
View Article and Find Full Text PDFNatl Sci Rev
August 2025
Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Achieving sustainable catalytic transformations requires synergistic optimization of solvent systems, catalytic motifs and energy inputs. Herein, we report a synergistic Pd/hydroquinone catalytic system that enables aerobic allylic C-H functions under ambient conditions (room temperature to 50°C, air) with high turnover frequency (TOF), using ethanol/water as a green medium. This strategy achieves unparalleled synthetic efficiency and demonstrates remarkable versatility across two pivotal transformations (alkylation and amination) involving over 90 products (up to 96% yield).
View Article and Find Full Text PDFJ Hazard Mater
September 2025
Department of Civil and Environmental Engineering, Nagoya Institute of Technology (Nitech), Gokiso-Cho, Showa-Ku, Nagoya, Aichi 466-8555, Japan; Institute of Materials and Systems for Sustainability, Department of Civil Engineering, Graduate School of Engineering, Nagoya University, Nagoya, Aichi 46
The popular soil fumigant 1,3-dichloropropene (1,3-D) is widely used worldwide and one of the top five most-used pesticides in the United States. However, 1,3-D is classified as a Group 2B carcinogen and understanding its environmental fate is important. The aerobic degradation pathway of 1,3-D, along with the involved microorganisms and enzymes have been comprehensively described, whereas anaerobic transformation and the associated functional players remain incompletely understood.
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