- Efficient synthesis of gem-dihydroperoxides with molecular oxygen and anthraquinone under visible light irradiation with fluorescent lamp
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We developed an efficient dihydroperoxidation protocol of various carbonyl compounds with molecular oxygen and anthraquinone in 2-propanol under visible light irradiation with a fluorescent lamp, which produced corresponding gem-dihydroperoxides in high yields.
- Cui, Lei,Tada, Norihiro,Okubo, Hiroaki,Miura, Tsuyoshi,Itoh, Akichika
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- Convenient synthesis of geminal bishydroperoxides by the reaction of ketones with hydrogen peroxide
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A convenient procedure was developed for the synthesis of geminal bishydroperoxides by the sulfuric acid-catalyzed reaction of ketones with hydrogen peroxide in THF. Gem-bishydroperoxides were prepared by the reactions of five- to seven-membered cycloalkanones without additional purification in 80-95% yields with a purity of more than 95%; their acyclic analogs were prepared in 43-72% yields. Copyright Taylor & Francis Group, LLC.
- Terent'ev,Platonov,Ogibin,Nikishin
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- Synthesis, crystal structure and anti-malarial activity of novel spiro- 1,2,4,5-tetraoxacycloalkanes
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(Cycloalkylidene)bishydroperoxides 3 react with 1,n-dihaloalkanes (n = 3-6) in the presence of CsOH-H2O in DMF affording the corresponding spiro- 1,2,4,5-tetraoxacycloalkanes 4 in moderate yields. Compound 4ba exhibits significant antimalarial activity in vitro against P. falciparum.
- Tsuchiya, Kaoru,Hamada, Yoshiaki,Masuyama, Araki,Nojima, Masatomo,McCullough, Kevin J.,Kim, Hye-Sook,Shibata, Yasuharu,Wataya, Yusuke
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- Perhydrolysis in Ethereal H2O2 Mediated by MoO2(acac)2: Distinct Chemoselectivity between Ketones, Ketals, and Epoxides
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Ketones, ketals, and epoxides were converted into corresponding hydroperoxides in high yields by reaction with ethereal H2O2 in the presence of a catalytic amount of MoO2(acac)2 with distinct (to date unattainable) chemoselectivity.
- An, Xiaosheng,Zha, Qinghong,Wu, Yikang
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supporting information
p. 1542 - 1546
(2019/02/26)
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- Activation of aqueous hydrogen peroxide for non-catalyzed dihydroperoxidation of ketones by azeotropic removal of water
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Cyclic and acyclic ketones were selectively converted to gem-dihydroperoxides in 72-99% yield with 30% aq. hydrogen peroxide by azeotropic distillation of water from the reaction mixture without any catalyst. The reactions were more selective than with 100% H2O2 and due to neutral conditions also less stable products could be obtained.
- Starkl Renar,Pe?ar,Iskra
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supporting information
p. 9369 - 9372
(2015/09/15)
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- Poly(N-vinylpyrrolidone)-H2O2 and poly(4-vinylpyridine)-H2O2 complexes: Solid H 2O2 equivalents for selective oxidation of sulfides to sulfoxides and ketones to gem-dihydroperoxides
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Complexes of poly(N-vinylpyrrolidone) (PVD) and poly(4-vinylpyridine) (PVP) with hydrogen peroxide have been prepared and their synthetic utility as solid H2O2 equivalents for the selective oxidation of sulfides to sulfoxides and ketones to gem-dihydroperoxides has been studied. These complexes are convenient and safe alternatives to H2O2 solutions and it is found that various symmetric as well as unsymmetrical sulfides undergo oxidation under mild conditions to provide the respective sulfoxides in high yields. A series of gem-dihydroperoxides were obtained from the corresponding ketones in good yields under ambient conditions. This journal is the Partner Organisations 2014.
- Surya Prakash,Shakhmin, Anton,Glinton, Kevin E.,Rao, Sneha,Mathew, Thomas,Olah, George A.
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supporting information
p. 3616 - 3622
(2014/07/08)
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- Oxidative cleavage of C=C bonds with singlet molecular oxygen generated from monoacetylated bishydroperoxides
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The oxidative cleavage of C=C bonds adjacent to aryl and alkyl moieties was efficiently achieved with monoacetylated bishydroperoxides. The main active oxidant used in this reaction was singlet molecular oxygen, which was generated in situ from the base-mediated fragmentation of monoacetylated bishydroper oxides. All the reactions proceeded smoothly at room temperature to furnish the respective carbonyl compounds in good yields within short reaction times. Georg Thieme Verlag Stuttgart · New York.
- Azarifar, Davood,Najminejad, Zohreh
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p. 1377 - 1382
(2013/07/26)
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- Synthesis of alkyl hydroperoxides via alkylation of gem -dihydroperoxides
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2-Fold alkylation of 1,1-dihydroperoxides, followed by hydrolysis of the resulting bisperoxyacetals, provides a convenient method for synthesis of primary and secondary alkyl hydroperoxides.
- Kyasa, Shivakumar,Puffer, Benjamin W.,Dussault, Patrick H.
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p. 3452 - 3456
(2013/06/26)
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- Synthesis and Antimalarial Activity of Dihydroperoxides and Tetraoxanes Conjugated with Bis(benzyl)acetone Derivatives
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Dihydroperoxides and tetraoxanes derived from symmetrically substituted bis(arylmethyl)acetones were synthesized in modest to good yields using several methods. Three of these compounds exhibit an important in vitro antimalarial activity (1.0μm≤IC50≤5.0μm) against blood forms of the human malaria parasite Plasmodium falciparum.
- Franco, Lucas Lopardi,de Almeida, Mauro Vieira,e Silva, Luiz Francisco Rocha,Vieira, Pedro Paulo Ribeiro,Pohlit, Adrian Martin,Valle, Marcelo Siqueira
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experimental part
p. 790 - 797
(2012/06/18)
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- Triflic acid-functionalized silica-coated magnetic nanoparticles as a magnetically separable catalyst for synthesis of gem-dihydroperoxides
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Triflic acid-functionalized silica-coated magnetic nanoparticles [γ-Fe2O3@SiO2-TfOH] were readily prepared and identified as an effictive catalyst for the transformation of aldehydes or ketones into their corresponding gem-dihydroperoxides with 30% aqueous hydrogen peroxide. The catalyst was easily separated by magnetic decantation and the recovered catalyst was reused for seven cycles without significant loss of catalytic activity. Copyright
- Liu, Yong-Hui,Deng, Jia,Gao, Jian-Wu,Zhang, Zhan-Hui
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experimental part
p. 441 - 447
(2012/04/04)
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- Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides
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The first singlet excited state of molecular oxygen (1O 2) is an important oxidant in chemistry, biology, and medicine. 1O2 is most often generated through photosensitized excitation of ground-state oxygen. 1O2 can also be generated chemically through the decomposition of hydrogen peroxide and other peroxides. However, most of these "dark oxygenations" require water-rich media associated with short 1O2 lifetimes, and there is a need for oxygenations able to be conducted in organic solvents. We now report that monoactivated derivatives of 1,1-dihydroperoxides undergo a previously unobserved fragmentation to generate high yields of singlet molecular oxygen (1O2). The fragmentations, which can be conducted in a variety of organic solvents, require a geminal relationship between a peroxyanion and a peroxide activated toward heterolytic cleavage. The reaction is general for a range of skeletal frameworks and activating groups and, via in situ activation, can be applied directly to 1,1-dihydroperoxides. Our investigation suggests the fragmentation involves rate-limiting formation of a peroxyanion that decomposes via a Grob-like process.
- Hang, Jiliang,Ghorai, Prasanta,Finkenstaedt-Quinn, Solaire A.,Findik, Ilhan,Sliz, Emily,Kuwata, Keith T.,Dussault, Patrick H.
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supporting information; scheme or table
p. 1233 - 1243
(2012/03/27)
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- Phosphomolybdic acid catalyzed synthesis of 1,2,4,5-tetraoxanes
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1,1-Dihydroperoxides were converted into 1,2,4,5-tetraoxanes through condensation with the corresponding ketones in 36-91% yields using phosphomolybdic acid as the catalyst and anhydrous MgSO4 as the water scavenger. Georg Thieme Verlag Stuttgart · New York.
- Yan, Xing,Chen, Jinglei,Zhu, Yun-Ting,Qiao, Chunhua
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body text
p. 2827 - 2830
(2012/01/03)
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- A facile catalyst-free synthesis of gem-dihydroperoxides with aqueous hydrogen peroxide
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gem-Dihydroperoxides were easily obtained from the corresponding carbonyl compounds in high yields through a catalyst-free method with aqueous H 2O2 (35%) in 1,2-dimethoxyethane at room temperature.
- Tada, Norihiro,Cui, Lei,Okubo, Hiroaki,Miura, Tsuyoshi,Itoh, Akichika
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supporting information; experimental part
p. 1772 - 1774
(2010/07/04)
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- An efficient synthesis of gem-dihydroperoxides with molecular oxygen and anthracene under light irradiation
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A new efficient dihydroperoxidation protocol of a wide variety of carbonyl compounds with molecular oxygen, anthracene, and 2-propanol under light irradiation afforded their corresponding gem-dihydroperoxides in high yields.
- Tada, Norihiro,Cui, Lei,Okubo, Hiroaki,Miura, Tsuyoshi,Itoh, Akichika
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supporting information; experimental part
p. 2383 - 2386
(2010/12/25)
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- A broadly applicable mild method for the synthesis of gem-diperoxides from corresponding Ketones or 1,3-dioxolanes
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Ketones or ketals were readily converted into the corresponding gem-dihydroperoxides in high yields by treatment with ethereal H 2O2 at ambient temperature in the presence of 2-5 mol % of phosphomolybdic acid.
- Li, Yun,Hao,Zhang, Qi,Wu, Yikang
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supporting information; experimental part
p. 1615 - 1618
(2009/08/07)
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- Broadly applicable synthesis of 1,2,4,5-tetraoxanes
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Re2O7 is a mild and efficient catalyst for the high-yielding condensation of 1,1-dihydroperoxides with ketones or aldehydes to form 1,2,4,5-tetraoxanes, including targets not easily prepared via existing methodology. When applied in
- Ghorai, Prasanta,Dussault, Patrick H.
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scheme or table
p. 213 - 216
(2009/06/20)
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- Mild and efficient Re(VII)-catalyzed synthesis of 1,1-dihydroperoxides
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(Chemical Equation Presented) Re2O7 in CH 3CN is a remarkably efficient and mild catalyst for the peroxyacetalization of ketones, aldehydes, or acetals by H2O 2 to generate 1,1-dihydroperoxides. Me3SiOReO3 and methyl rhenium trioxide (MTO) are also effective catalysts under these reaction conditions.
- Ghorai, Prasanta,Dussault, Patrick H.
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supporting information; body text
p. 4577 - 4579
(2009/05/11)
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- Oxidation of cycloalkanones with hydrogen peroxide: an alternative route to the Baeyer-Villiger reaction. Synthesis of dicarboxylic acid esters
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The acid-catalyzed oxidation of cycloalkanones C5-C8 and C12 with hydrogen peroxide in alcohols was performed, and dicarboxylic acid esters were obtained as the major products in 53-70% yields. In the first step, geminal bishydroperoxides are generated from five-to-seven-membered cyclic ketones. The Baeyer-Villiger reaction is a side process accompanied by the formation of ω-hydroxycarboxylic acid esters.
- Terent'ev, Alexander O.,Platonov, Maxim M.,Kashin, Alexey S.,Nikishin, Gennady I.
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p. 7944 - 7948
(2008/12/21)
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- Synthesis of spiro-1,2-dioxolanes and their activity against Plasmodium falciparum
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Artemisinin-derived compounds play an integral role in current malaria chemotherapy. Given the virtual certainty of emerging resistance, we have investigated spiro-1,2-dioxolanes as an alternative scaffold. The endoperoxide functionality was generated by the SnCl4-mediated annulation of a bis-silylperoxide and an alkene. The first set of eight analogs gave EC50 values of 50-150 nM against Plasmodium falciparum 3D7 and Dd2 strains, except for the carboxylic acid analog. A second series, synthesized by coupling a spiro-1,2-dioxolane carboxylic acid to four separate amines, afforded the most potent compound (EC50 ~5 nM).
- Martyn, Derek C.,Ramirez, Armando P.,Beattie, Meaghan J.,Cortese, Joseph F.,Patel, Vishal,Rush, Margaret A.,Woerpel,Clardy, Jon
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scheme or table
p. 6521 - 6524
(2009/10/02)
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- The effect of iodine on the peroxidation of carbonyl compounds
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(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.
- Zmitek, Katja,Zupan, Marko,Stavber, Stojan,Iskra, Jernej
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p. 6534 - 6540
(2008/02/10)
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- Iodine as a catalyst for efficient conversion of ketones to gem-dihydroperoxides by aqueous hydrogen peroxide
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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 H2O2) 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.
- Zmitek, Katja,Zupan, Marko,Stavber, Stojan,Iskra, Jernej
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p. 2491 - 2494
(2007/10/03)
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- NOVEL COMPOUNDS AND ANTIMALARIALS
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The present invention is to provide an antimalarial agent having excellent antimalarial activity with little side effects, in particular, having remarkable antimalarial activity against drug-resistant malaria parasites, and being capable of increasing solubilitiy not only to organic solvent including olive oil, but also to water, and therefore, being usable not only as oral drugs but also as injectable solutions. The antimalarial agent of the present invention contains a compound represented by the following general formula (I) [wherein Z represents an unsubstituted or optionally substituted alicyclic hydrocarbon group, R0 represents a water-soluble functional group, m represents any one of integers of from 0 to 6, n represents any one of integers of from 0 to 10.].
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- Synthesis of 1,2-dioxolanes by annulation reactions of peroxycarbenium ions with alkenes
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(Chemical Equation Presented) The annulation reactions of alkenes with peroxycarbenium ions enable the synthesis of a variety of functionalizable 1,2-dioxolanes. Triethysilyl-protected peroxycarbenium ions proved to be optimal for the annulation reaction. Using this method, plakinic acid analogues can be synthesized in three steps from the corresponding ketone and alkene.
- Ramirez, Armando,Woerpel
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p. 4617 - 4620
(2007/10/03)
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- Synthesis and antimalarial activity of novel medium-sized 1,2,4,5-tetraoxacycloalkanes
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CsOH- or Ag2O-mediated cycloalkylation of (alkylidene)bisperoxides 3 and 1,n-dihaloalkanes (n = 3-8) provided the corresponding medium-sized 1,2,4,5-tetraoxacycloalkanes 4-8 in moderate yields. Subsequent evaluation of the antimalarial activity of the cyclic peroxides 4-8 in vitro and in vivo revealed that 1,2,6,7-tetraoxaspiro[7.11]nonadecane 4a has considerable potential as a new, inexpensive, and potent antimalarial drug.
- Kim,Nagai,Ono,Begum,Wataya,Hamada,Tsuchiya,Masuyama,Nojima,McCullough
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p. 2357 - 2361
(2007/10/03)
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