Reaction modes and mechanism in indolizine photooxygenation reactions
Li, Y; Hu, HY; Ye, JP; Fun, HK; Hu, HW; Xu, JH
AbstractPhotooxygenations of 1,2-, 1,3-, and 2,3-di- and 1,2,3-trisubstituted indolizines 1a-1f under different reaction conditions in methanol and acetonitrile have been investigated to establish the general reaction pattern and mechanism in indolizine photooxygenation in view of the influence of the ring substituents and substitution pattern. Photooxygenations of 1-acyl-2-phenylindolizines 1a and 1b and 1,3-dibenzoyl-2-phenylindolizine (1d) are self-sensitized, while those of 1-(p-nitrobenzoyl)2-phenylindolizine (1c) and 2-phenyl-3-(p-chlorobenzoyl)indolizine (1e) need to be sensitized by rose bengal (RB) or methylene blue (MB). These reactions proceed via a singlet oxygen mechanism yet follow different pathways in methanol and in acetonitrile, with peroxidic zwitterion D (in methanol) and dioxetane E across the indolizine C2-C3 bond (in acetonitrile) as the intervening intermediates. Methanol trapping of the peroxidic zwitterion results in C3-N bond cleavage and pyrrole ring opening to give the corresponding (E)- and (Z)-3-(2-pyridinyl)-3-benzoylpropenoic acid methyl esters (2 and 3) and 4-(2-pyridinyl)-3-phenyl-5-aryl-5-hydroxyfuran-2-one (4) as products in methanol, while O-O bond homolysis of the dioxetane furnishes 3-(2-pyridinyl)-3-benzoyl-2-phenyloxirane-2-carboxaldehyde (6) and 1-(6-methyl-2-pyridinyl)-2-phenylethanedione (5) as products in acetonitrile. 3-Benzoyl-1-indolizinecarboxylic acid methyl ester (If) is unreactive toward singlet oxygen; however, it could be photooxygenated under electron transfer conditions with 9,10-dicyanoanthracene (DCA) as a sensitizer. This reaction takes place by the combination of the indolizine cation radical with the superoxide anion radical (or molecular oxygen) to give the pyridine ring oxidized methyl 3-benzoyl-5-methoxy-8-hydroxy-1-indolizinecarboxylate (9f), dimethyl 2-(2-pyridinyl)fumarate (8f), and dimethyl 2-(2-pyridinyl)maleate (7f) as products.
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WOS IDWOS:000220506200015
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Document Type期刊论文
Corresponding AuthorXu, JH
Affiliation1.Nanjing Univ, Dept Chem, Nanjing 210093, Peoples R China
2.Chinese Acad Sci, Inst Chem, Beijing 100080, Peoples R China
3.Univ Sains Malaysia, Sch Phys, Xray Crystallog Unit, George Town, Malaysia
Recommended Citation
GB/T 7714
Li, Y,Hu, HY,Ye, JP,et al. Reaction modes and mechanism in indolizine photooxygenation reactions[J]. JOURNAL OF ORGANIC CHEMISTRY,2004,69(7):2332-2339.
APA Li, Y,Hu, HY,Ye, JP,Fun, HK,Hu, HW,&Xu, JH.(2004).Reaction modes and mechanism in indolizine photooxygenation reactions.JOURNAL OF ORGANIC CHEMISTRY,69(7),2332-2339.
MLA Li, Y,et al."Reaction modes and mechanism in indolizine photooxygenation reactions".JOURNAL OF ORGANIC CHEMISTRY 69.7(2004):2332-2339.
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