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Scientific Reports May 2015The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes...
The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64](4+)ยท4e(-), through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry.
PubMed: 26020413
DOI: 10.1038/srep10366 -
Scientific Reports Nov 2020Dimer radical ions of aromatic molecules in which excess charge is localized in a pair of rings have been extensively investigated. While dimer radical cations of...
Dimer radical ions of aromatic molecules in which excess charge is localized in a pair of rings have been extensively investigated. While dimer radical cations of aromatics have been previously produced in the condensed phase, the number of molecules that form dimer anions is very limited. In this study, we report the formation of intramolecular dimer radical ions (cations and anions) of diphenyl sulfone derivatives (DPs) by electron beam pulse radiolysis in the liquid phase at room temperature. The density functional theory (DFT) calculations also showed the formation of the dimer radical ions. The torsion barrier of the phenyl ring of DPs was also calculated. It was found that the dimer radical ions show the larger barrier than the neutral state. Finally, stability of the dimer radical anion is dependent on not only the inductive effect of the sulfonyl group but the conjugation involving the d-orbital of the S atom and the phenyl rings.
PubMed: 33188267
DOI: 10.1038/s41598-020-76907-4 -
The Journal of Physical Chemistry. B Mar 2016
Topics: Cations; Free Radicals; Guanine; Protons; Pulse Radiolysis; Spectrum Analysis, Raman
PubMed: 26931377
DOI: 10.1021/acs.jpcb.5b12607