579-74-8Relevant articles and documents
-OH-Induced shift from carbon to oxygen acidity in the side-chain deprotonation of 2-, 3- and 4-methoxybenzyl alcohol radical cations in aqueous solution: Results from pulse radiolysis and DFT calculations
Baciocchi, Enrico,Bietti, Massimo,Ercolani, Gianfranco,Steenken, Steen
, p. 613 - 618 (2003)
DFT calculations have been carried out for 2-, 3- and 4-methoxybenzyl alcohol radical cations (1·+, 3·+ and 4·+, respectively) and the α-methyl derivatives 2·+ and 5·+ using the UB3LYP/6-31G(d) method. The theoretical results have been compared with the experimental rate constants for deprotonation of 1·+-5·+ under acidic and basic conditions. In acidic solution, the decay of 1·+-5·+ proceeds by cleavage of the C-H bond, while in the presence of -OH all the radical cations undergo deprotonation from the α-OH group. This pH-dependent change in mechanism has been interpreted qualitatively in terms of simple frontier molecular orbital theory. The -OH induced α-O-H deprotonation is consistent with a charge controlled reaction, whereas the C-H deprotonation, observed when the base is H2O, appears to be affected by frontier orbital interactions.
Selective electrochemical oxidation of aromatic hydrocarbons and preparation of mono/multi-carbonyl compounds
Li, Zhibin,Zhang, Yan,Li, Kuiliang,Zhou, Zhenghong,Zha, Zhenggen,Wang, Zhiyong
, p. 2134 - 2141 (2021/09/29)
A selective electrochemical oxidation was developed under mild condition. Various mono-carbonyl and multi-carbonyl compounds can be prepared from different aromatic hydrocarbons with moderate to excellent yield and selectivity by virtue of this electrochemical oxidation. The produced carbonyl compounds can be further transformed into α-ketoamides, homoallylic alcohols and oximes in a one-pot reaction. In particular, a series of α-ketoamides were prepared in a one-pot continuous electrolysis. Mechanistic studies showed that 2,2,2-trifluoroethan-1-ol (TFE) can interact with catalyst species and generate the corresponding hydrogen-bonding complex to enhance the electrochemical oxidation performance. [Figure not available: see fulltext.]
Metal- And additive-free C-H oxygenation of alkylarenes by visible-light photoredox catalysis
García Manche?o, Olga,Kuhlmann, Jan H.,Pérez-Aguilar, María Carmen,Piekarski, Dariusz G.,Uygur, Mustafa
supporting information, p. 3392 - 3399 (2021/05/21)
A metal- and additive-free methodology for the highly selective, photocatalyzed C-H oxygenation of alkylarenes under air to the corresponding carbonyls is presented. The process is catalyzed by an imide-acridinium that forms an extremely strong photooxidant upon visible light irradiation, which is able to activate inert alkylarenes such as toluene. Hence, this is an easy to perform, sustainable and environmentally friendly oxidation that provides valuable carbonyls from abundant, readily available compounds.
