2459-24-7Relevant articles and documents
Acceptorless Dehydrogenation of Hydrocarbons by Noble-Metal-Free Hybrid Catalyst System
Fuse, Hiromu,Kojima, Masahiro,Mitsunuma, Harunobu,Kanai, Motomu
, p. 2042 - 2045 (2018/04/16)
A hybrid catalysis that comprises an acridinium photoredox catalyst, a thiophosphate organocatalyst, and a nickel catalyst-enabled acceptorless dehydrogenation of hydrocarbons is reported. The cationic nickel complex played a critical role in the reactivity. This is the first example of acceptorless dehydrogenation of hydrocarbons by base metal catalysis under mild reaction conditions of visible light irradiation at room temperature.
Facile preparation of aromatic esters from aromatic bromides with ethyl formate or DMF and molecular iodine via aryllithium
Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
experimental part, p. 4701 - 4709 (2012/07/28)
Various aromatic bromides were treated with n-BuLi and subsequently with ethyl formate, followed by the reaction with ethanol and molecular iodine in the presence of K2CO3 to provide the corresponding aromatic ethyl esters in good yields. Moreover, aromatic bromides could be transformed into the corresponding aromatic methyl esters in good yields by the treatment with n-BuLi and subsequently with DMF, followed by the reaction with methanol, molecular iodine, and K2CO3. Some aromatics could be also converted into the corresponding aromatic esters in good yields by the treatment with n-BuLi, and subsequently with ethyl formate or DMF, followed by the reaction with molecular iodine and K2CO3. The present reactions offer a novel route for the transition-metal-free, carbon-monoxide-free, and therefore environmentally benign one-pot conversion of aromatic bromides and aromatics into aromatic esters.
Dependence of intramolecular dissociative electron transfer rates on driving force in Donor-Spacer-Acceptor systems
Antonello, Sabrina,Maran, Flavio
, p. 5713 - 5722 (2007/10/03)
The voltammetric reduction of a series of phenyl-substituted 4- benzoyloxy-1-methylcyclohexyl bromides has been investigated in DMF. The reduction leads to the cleavage of the C-Br bond. On a thermodynamic ground, the direct reduction of the tertiary C-Br function is easier than that of the selected benzoates by at least 0.5 V. However, since the direct reduction of bromides is affected by a large activation overpotential, the electron is first located in the benzoate moiety. The rate constant for the following exergonic intramolecular dissociative electron transfer was determined by kinetic analysis of the cyclic voltammetry curves. The intermolecular rate constants for the reaction between the radical anions of methyl benzoates and 4-tert-butyl-1-methylcyclohexyl bromide were also determined and found to correlate very well with related literature data pertaining to tert-butyl bromide. The intramolecular rate constants were found to be more sensitive to variation of driving force than the corresponding intermolecular data. This result can be attributed to a shift of the center of the π* orbital of the radical anion donor away from the acceptor moiety, the shift being larger for the most easily reduced donors. The resulting distance increase is therefore envisaged as responsible for a more rapid rate drop, compared to the intermolecular pattern, when smaller driving forces are considered.
