Iodine as a Catalyst for Efficient Conversion of Ketones to gem-Dihydroperoxides by Aqueous Hydrogen Peroxide

Abstract

Iodine has been shown to be an efficient catalyst for the selective dihydroperoxidation of ketones with aqueous hydrogen peroxide. Ketones were directly converted to their corresponding gem-dihydroperoxides using a "green" oxidant (30% aq H(2)O(2)) and a simple catalyst (iodine) under neutral conditions in acetonitrile. The yield of hydroperoxidation of various cyclic ketones was 60-98% including androstane-3,17-dione, and acyclic ketones were converted with a similar efficiency. [reaction: see text]

Oxidative Halogenation with “Green” Oxidants: Oxygen and Hydrogen Peroxide

“…The selective activation and departure of an OH group by iodine in the presence of an OOH group had already been observed during the peroxidation of carbonyl compounds. [113,114] The effect of acid has also been studied in the iodination of carbonyl compounds. Such reactions require a strong acid, and the best yields for the iodination of acetophenone to 91 were obtained using H 2 SO 4 in CH 3 CN.…”

A novel and efficient approach for the synthesis of new halo substituted 2-arylpyrazolo[4,3-c] coumarin derivatives

“…The use of iodine for synthetic purpose has gained significant importance. The negligible toxicity associated with iodine, in conjunction with ease of handling, readily availability, low cost and mild reaction conditions employed has resulted in its application in an increasing number of diverse transformations [18][19][20][21][22][23][24][25][26][27][28]. In continuation of our research programme using I2/DMSO as an efficient catalytic system for oxidation of pyrazoline to pyrazole [29], deallylation and preparation of flavones from 2'allyloxychalcones [30] and oxidation of dihydroflavone [31], here, we wish to report some new halo substituted 2arylpyrazolo [4,3-c]coumarins under mild condition.…”

Mild oxidative aromatization of 1,4-dihydropyridines with trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxalane promoted by ammonium bromide/HOAc in water/MeCN

“…Thus, as regards the importance of pyridines, the development of a simple, efficient, mild, and versatile method for the oxidation of 1,4-DHP is of interest in organic methodology. Recently, gem-dihydroperoxides have been synthesized and have been used for oxidation reactions Bunge, Hamann, McCalmont, & Liebscher, 2009;Das, Krishnaiah, Veeranjaneyulu, & Ravikanth, 2007;Das, Veeranjaneyulu, Krishnaiah, & Balasubramanyam, 2008;Ghorai & Dussault, 2008;Li, Hao, Zhang, & Wu, 2009;Žmitek, Zupan, Stavber, & Iskra, 2006;Žmitek, Zupan, Stavber, & Iskra, 2007). We have synthesized trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxalane (Scheme 1) and used it as a powerful oxidant in some organic reactions (Azarifar & Khosravi, 2010a;Azarifar & Khosravi, 2010b;Azarifar, Khosravi, & Soleimanei, 2009;Azarifar, Najminejad, & Khosravi, 2013;Khosravi, 2014;Khosravi, 2015;Khosravi & Kazemi, 2012;Khosravi, Mobinikhaledi, Kazemi, Azarifar, & Rahmani, 2014;Khosravi, Pirbodaghi, Kazemi, & Asghari, 2015).…”