4186-27-0Relevant academic research and scientific papers
Synthesis and asymmetric resolution of α-azido-peroxides
Pramanik, Suman,Ghorai, Prasanta
supporting information, p. 3832 - 3835 (2013/09/02)
An unprecedented synthesis of α-azido-peroxides has been developed using an FeCl3-catalyst starting from carbonyl, TMS-azide, and hydroperoxide. Further, a base promoted decomposition of synthesized secondary α-azido-peroxides to provide the corresponding tert-butyl esters has been disclosed. Finally, an asymmetric kinetic resolution of such α-azido-peroxides has also been developed to provide chiral α-azido-peroxides in excellent enantiopurity.
The effect of iodine on the peroxidation of carbonyl compounds
Zmitek, Katja,Zupan, Marko,Stavber, Stojan,Iskra, Jernej
, p. 6534 - 6540 (2008/02/10)
(Chemical Equation Presented) Peroxidation of ketones and aldehydes with iodine as a catalyst was studied. Ketones reacted with 30% aq hydrogen peroxide in the presence of 10 mol % of iodine to yield gem-dihydroperoxides in acetonitrile and hydroperoxyketals in methanol. The yield of hydroperoxidation of various cyclic ketones was 60-98%, including androstane-3,17-dione, while acyclic ketones were converted with a similar efficiency. Aromatic aldehydes were also converted to gem-dihydroperoxides with hydrogen peroxide and iodine as catalyst in acetonitrile and to hydroperoxyacetal in methanol, while the reactivity of aliphatic ones remained the same as in noncatalyzed reactions. tert-Butylhydroperoxide reacted in a similar manner, giving the corresponding perether derivatives. A study was also made of the relative kinetics of dihydroperoxidation from which the Hammet equation gave a reaction constant (ρ) of -2.76, indicating the strong positive charge development in the transition state and the important role of rehybridization in the conversion of hydroperoxyhemiketal to gem-dihydroperoxide. In acetonitrile, the iodine catalyst is apparently able to discriminate between the elimination of a hydroxy, methoxy, and hydroperoxy group and addition of water, methanol, and H2O2 to a carbonyl group.
A Facile Method for the Oxidation of Aldehydes to Carboxylic Acids via Acetal-type Diperoxides
Mukaiyama, Teruaki,Miyoshi, Norikazu,Kato, Jun-ichi,Ohshima, Masahiro
, p. 1385 - 1388 (2007/10/02)
In the presence of a catalytic amount of trityl perchlorate, aldehydes smoothly react with t-butyl trimethylsilyl peroxide to give the acetal-type diperoxides in good yields.Treatment of these diperoxides with piperidine at 90 degC or the aqueous solution of CuSO4 and L-ascorbic acid at room temperature gave the corresponding carboxylic acids in good yields.
