A unique peroxide formation based on the Mn(III)-catalyzed aerobic oxidation

Kumabe, Ryoukou; Nishino, Hiroshi

doi:10.1016/j.tetlet.2003.11.054

Cited by 52 publications

(12 citation statements)

References 30 publications

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“…The ORTEP drawing of 2g is shown in Figure 1 . The intramolecular hydrogen-bonding in 2g could be visualized between the terminal hydroperoxy oxygen and the carbonyl oxygen, O(4)-O(1) (2.705 Å) [ 32 , 33 , 37 , 38 , 39 , 40 , 42 ]. The other hydroperoxides obtained from the aerobic oxidation showed similar spectroscopic features.…”

Section: Resultsmentioning

confidence: 99%

“…In connection with our current investigation of the Mn(OAc) 3 -assisted aerobic oxidation [ 31 , 32 , 33 , 34 , 35 , 36 ], we found the double hydroperoxyalkylaton of barbituric acids [ 37 ], pyrazolidine-3,5-diones ( Scheme 1 ) [ 38 , 39 ], 4-hydroxy-1 H -quinolin-2-ones [ 40 ], and tetronic acid [ 41 ]. The reaction could not be stopped at the monohydroperoxyalkylation stage.…”

Section: Introductionmentioning

confidence: 94%

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Mn(III)-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

et al. 2011

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The Mn(III)-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

Mn(III)-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

et al. 2011

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“…For further examples and applications of related chemistry from the Nishino group (see ref. [41][42][43][44][45][46][47][48][49][50][51].…”

Section: Exploitation Of Can (Ceric Ammonium Nitrate) Promoted Singlementioning

confidence: 99%

Treasures old and new: what we can learn regarding the macrocyclic problem from past and present efforts in natural product total synthesis

et al. 2020

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“…[4][5][6][7][8][9][10][11][12][13][14][15] From the viewpoint for the drug design, it is also demanded to synthesize hitherto unknown unnatural MeQone derivatives and to develop new methods for functionalization of the MeQone framework. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Especially, modification of the pyridone moiety in the MeQone is highly important because most of the naturally occurring MeQones have substituents at the 3 and/or the 4-position. Mainly used methods for functionalization of the MeQone involve the activation by the pre-introduced substituents such as hydroxyl, alkoxyl and amino groups, [4][5][6][7][8][9][10][11][12][13][14][15] which compose partial structures of newly constructed skeleton.…”

mentioning

confidence: 99%

“…Meanwhile, direct functionalization methods of MeQone were recently attracted. [16][17][18][19][20][21][22][23][24][25][26][27][28][29] As one of the methodologies, Fujita and co-workers prepared phenanthridine derivatives by Diels-Alder reaction of electron-rich dienes with MeQone having an electron-withdrawing group at the 3 or 4-position. [30][31][32] In our course of study on electron-deficient quinolones, 1-methyl-3,6,8-trinitro-2-quinolone (TNQ) was found to be highly reactive, which realized direct functionalization of the MeQone.…”

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Synthesis of Unnatural 1-Methyl-2-quinolone Derivatives

Asahara

Katayama

Tohda

et al. 2004

CHEMICAL & PHARMACEUTICAL BULLETIN

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The 1-methyl-2-quinolone (MeQone) skeleton has been found in more than 300 quinoline alkaloids those are mostly isolated from the Rutaceae family. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Since these alkaloids show physiological activities, many researchers have energetically studied the isolation, the structural determination and total syntheses of quinoline alkaloids containing the MeQone skeleton. [4][5][6][7][8][9][10][11][12][13][14][15] From the viewpoint for the drug design, it is also demanded to synthesize hitherto unknown unnatural MeQone derivatives and to develop new methods for functionalization of the MeQone framework. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Especially, modification of the pyridone moiety in the MeQone is highly important because most of the naturally occurring MeQones have substituents at the 3 and/or the 4-position. Mainly used methods for functionalization of the MeQone involve the activation by the pre-introduced substituents such as hydroxyl, alkoxyl and amino groups, [4][5][6][7][8][9][10][11][12][13][14][15] which compose partial structures of newly constructed skeleton. Meanwhile, direct functionalization methods of MeQone were recently attracted. [16][17][18][19][20][21][22][23][24][25][26][27][28][29] As one of the methodologies, Fujita and co-workers prepared phenanthridine derivatives by Diels-Alder reaction of electron-rich dienes with MeQone having an electron-withdrawing group at the 3 or 4-position. [30][31][32] In our course of study on electron-deficient quinolones, 1-methyl-3,6,8-trinitro-2-quinolone (TNQ) was found to be highly reactive, which realized direct functionalization of the MeQone.33) The steric repulsion between the 8-nitro and the 1-methyl groups activates the pyridone ring of TNQ, which reveals nitroalkene property rather than aromatic one. 34)When TNQ was allowed to react with tertiary amine in acetonitrile, dimer of TNQ connected at the 3-and 4Ј-positions was obtained at room temperature, and denitration on the pyridone ring occurred at the elevated temperature leading to 1.35) On the other hand, 4-functionalized 6,8-dinitro-2-quinolones, were readily formed upon treatment of TNQ with 1,3-dicarbonyl compounds in the presence of triethylamine, in which regioselective C-C bond formation at the 4-position is achieved. 33) Although the present cine-substitution is useful for direct functionalization of the quinolone ring, only 1,3-dicarbonyl compounds were usable. Thus, it is one of the important projects to enable the employment other nucleophiles, which provides a new methodology for the quinolone chemistry. Since we succeed to introduce a variety of acylmethyl groups at the 4-position of the MeQone skeleton, results will be represented in this paper. Results and DiscussionEnamines were employed as the carbon nucleophiles instead of 1,3-dicarbonyl compounds. When TNQ was treated with 1-morpholino-1-phenylethene 2a in the presence of water at room temperature, 4-benzoylmethyl-6,8-dinitro-2-quinolone 3a was isol...

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A unique peroxide formation based on the Mn(III)-catalyzed aerobic oxidation

Cited by 52 publications

References 30 publications

Mn(III)-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

Mn(III)-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

Treasures old and new: what we can learn regarding the macrocyclic problem from past and present efforts in natural product total synthesis

Synthesis of Unnatural 1-Methyl-2-quinolone Derivatives

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