An electrochemical 'redox-relay' system has been developed which allows the generation of C-centered radicals. Intermolecular 'tin-like' radical reactions can subsequently be conducted under the most benign of conditions. The yields and efficiency of the processes are competitive and even superior in most cases to comparable conditions with tributyltin hydride. The use of air and electricity as the promotor (instead of a tin or other reagent) combined with the aqueous reaction media make this a clean and 'green' alternative to these classic C-C bond forming processes.
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http://dx.doi.org/10.1039/d0sc01694b | DOI Listing |
PLoS One
January 2025
Departamento de Reología y Mecánica de Materiales, Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México Ciudad Universitaria, Ciudad de México, México.
A hybrid coating made of poly (methyl methacrylate) with SiO2-TiO2 particles (PMMA/SiO2-TiO2) has been developed for use as a coating on nanosatellites, evaluating its resistance to high vacuum by quantifying its weight loss. The coating was applied on an Al 7075 aluminum substrate used for the aerospace sector. PMMA/SiO2-TiO2 hybrid coatings were prepared using sol-gel reaction in situ assisted with sonochemistry.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Department of Chemistry, University of Hawai'i at Ma̅noa, Honolulu, Hawaii 96822, United States.
What if an experiment could combine the power of cycloaddition and cross-coupling with the formation of an aromatic molecule in a single collision? Crossed molecular beam experiments augmented with electronic structure and statistical calculations provided compelling evidence on a novel radical route involving 1,3-butadiynyl (HCCCC; X∑) radicals synthesizing (substituted) arylacetylenes in the gas phase upon reactions with 1,3-butadiene (CHCHCHCH; XA) and 2-methyl-1,3-butadiene (isoprene; CHC(CH)CHCH; XA'). This elegant mechanism merges two previously disconnected concepts of cross-coupling and cycloaddition-aromatization in a single collision event via the formation of two new C(sp)-C(sp) bonds and bending the 180° moiety of the linear 1,3-butadiynyl radical out of the ordinary by 60° to 120°. In addition to its importance to fundamental organic chemistry, this unconventional mechanism links two previously separated routes of gas-phase molecular mass growth processes of polyacetylenes and polycyclic aromatic hydrocarbons (PAHs), respectively, in low-temperature environments such as in cold molecular clouds like the Taurus Molecular Cloud (TMC-1) and in hydrocarbon-rich atmospheres of planets and their moons such as Titan, which revises the established understanding of low-temperature molecular mass growth processes in the Universe.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Beijing University of Chemical Technology, State Key Laboratory of Organic-Inorganic Composites, 15 North Third Ring Road East, 37830, Beijing, CHINA.
Polymers with strong electron-withdrawing groups (e.g., cyano-containing polymers) are attractive for a wide range of applications due to their high dielectric constant and outstanding electrochemical stability.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
The direct synthesis of C(sp)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there is a strong impetus to develop new methods by which to access sp-rich molecules from commercial feedstocks, such as alkenes.
View Article and Find Full Text PDFChem Asian J
January 2025
National Chemical Laboratory CSIR, Chemical Engineering Division, Dr. Homi Bhabha Road, 411008, Pune, INDIA.
Regioselective C-H difluoroalkylation of diverse 2-pyridones with ethyl bromodifluoroacetates and bromodifluoroacetamides is accomplished by using a (dppf)NiCl2 catalyst under mild conditions. This efficient protocol could deliver a variety of C-3 difluoroalkylated pyridones with the tolerance of a range of highly susceptible functionalities, such as -Cl, -Br, -I, -COMe, -CN, -NMe2 and -NO2, including heteroarenes like pyridinyl, furanyl, thiophenyl and carbazolyl moieties. A preliminary mechanistic study suggests the radical pathway for the reaction involving fluoroalkyl radical intermediate.
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