二茂铁基吡喃酮并喹啉化合物的高效合成及其抗氧化性能

Efficient synthesis and antioxidation activities of ferrocenylpyrano-fused quinolines

摘要:

本文采用Ce(OTf)3和Sc(OTf)3复合催化4-甲基-7-氨基苯并吡喃酮、芳香醛和二茂铁基乙炔发生Povarov三组分反应(Povarov-3CR)，高效合成了15种已知二茂铁基吡喃酮并喹啉化合物，产率为40.0%~66.8%; 采用1H NMR、13C NMR和HR-MS(ESI)表征产物分子结构，通过抑制HO·和还原型谷胱甘肽自由基(GS·)引发DNA氧化反应测试比较化合物抗氧化活性，探究取代基种类、位置和数目对二茂铁基吡喃酮并喹啉抗氧化性能的影响. 结果表明：抑制HO·引发DNA氧化反应测试显示，15个目标化合物相对空白硫代巴比妥酸活性物质吸光度百分数(TBARS百分数)为36.6%~83.3%；抑制GS·引发DNA氧化反应体系测试显示，15个目标化合物TBARS百分数达22.9%~67.2%；在分子中引入推电子基团(-N(CH3)2、-OCH3和-OH)均能提升目标化合物的抗氧化能力，而吸电子基团(-Cl)有降低抗氧化能力作用；二茂铁基吡喃酮并喹啉化合物的抗氧化性能优于二茂铁基喹啉化合物，是一类潜在的强抗氧化剂.

Abstract:

Fifteen known ferrocenylpyrano-fused quinolines were synthesized efficiently via three-component Povarov reaction of 4-methyl-7-aminobenzopyranone, aromatic aldehydes, and ferrocenyl acetylene in the presence of cerium trifluoromethylsulfonate (Ce(OTf)3) and scandium trifluoromethylsulfonate (Sc(OTf)3), with yields ranging from 40.0% to 66.8%. The structures of the compounds were characterized by 1H NMR, 13C NMR, and HR-MS (ESI). The antioxidant activities of the compounds were evaluated by inhibiting oxidation reaction of DNA induced by hydroxyl radical (HO·) and reductive glutathione radical (GS·), and the effects of the type, position and number of substituents on the antioxidant abilities of ferrocenylpyrano-fused quinolines were investigated. The results showed that the fifteen target compounds exhibited strong radical scavenging activities to protect DNA against oxidation induced by HO· and GS·. The absorbance percentages of thiobarbituric acid reactive substances (TBARS) of the fifteen target compounds were 36.6%~83.3% in inhibiting HO· induced oxidation of DNA, and 22.9%~67.2% in inhibiting GS· induced oxidation of DNA, respectively. The antioxidant activity could be further enhanced by introduction of electron-donating groups (such as -N(CH3)2, -OCH3, and -OH) in ferrocenylpyrano-fused quinolines structures, while antioxidant activity was reduced when electron-withdrawing group (-Cl) was introduced. The ferrocenylpyrano-fused quinolines exhibited better antioxidant performance than ferrocenyl quinolines and are potential powerful antioxidants.