title: Mn(III)-initiated facile oxygenation of heterocyclic 1,3-dicarbonyl compounds.
abstract: 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.
authors.affiliation: Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan.
authors.forename: Md Taifur
authors.initials: MT
authors.lastname: Rahman
authors.forename: Md Aminul
authors.initials: MA
authors.lastname: Haque
authors.forename: Hikaru
authors.initials: H
authors.lastname: Igarashi
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishino
mesh_terms: D000577:Amides / Q000737:chemistry; D000818:Animals; D006367:HeLa Cells; D006571:Heterocyclic Compounds / Q000737:chemistry* / Q000494:pharmacology; D006801:Humans; D006861:Hydrogen Peroxide / Q000737:chemistry / Q000494:pharmacology; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010963:Plasmodium falciparum / Q000187:drug effects; D015363:Quinolones / Q000737:chemistry / Q000494:pharmacology
chemical_list: D000577:Amides; D006571:Heterocyclic Compounds; D015363:Quinolones; D008345:Manganese; D006861:Hydrogen Peroxide; D010100:Oxygen
references.citation: J Am Chem Soc. 2008 May 14;130(19):6068-9
references.pmid: 18422316
references.citation: J Am Chem Soc. 2010 Sep 29;132(38):13533-44
references.pmid: 20809620
references.citation: J Am Chem Soc. 1971 Jun 30;93(13):3299-301
references.pmid: 5559600
references.citation: Bioorg Med Chem. 2007 Jun 1;15(11):3912-8
references.pmid: 17395468
references.citation: Org Lett. 2004 Mar 4;6(5):691-4
references.pmid: 14986951
references.citation: Org Lett. 2011 Aug 5;13(15):4116-9
references.pmid: 21732596
references.citation: Arzneimittelforschung. 1987 Nov;37(11):1229-32
references.pmid: 3440030
references.citation: J Am Chem Soc. 2005 Jun 15;127(23):8292-3
references.pmid: 15941256
references.citation: J Org Chem. 2003 Feb 21;68(4):1358-66
references.pmid: 12585875
references.citation: Mol Pharmacol. 1985 Jan;27(1):109-14
references.pmid: 3917545
references.citation: Science. 2005 Apr 15;308(5720):395-8
references.pmid: 15831754
references.citation: J Agric Food Chem. 2005 Nov 30;53(24):9566-70
references.pmid: 16302778
references.citation: J Med Chem. 1987 Mar;30(3):563-7
references.pmid: 3102742
references.citation: Org Biomol Chem. 2011 Jul 7;9(13):4873-81
references.pmid: 21607276
references.citation: Org Lett. 2003 Aug 7;5(16):2887-90
references.pmid: 12889900
references.citation: J Med Chem. 1992 Sep 4;35(18):3423-5
references.pmid: 1326635
references.citation: J Org Chem. 2004 Aug 20;69(17):5646-51
references.pmid: 15307735