Kulkarni Manohar V, Kulkarni Geeta M, Lin Chao-Hsiung, Sun Chung-Ming
Department of Applied Chemistry, National Chiao-Tung University, Hsinchu 300-50, Taiwan.
Curr Med Chem. 2006;13(23):2795-818. doi: 10.2174/092986706778521968.
Coumarins, also referred as benzopyran-2-ones, and their corresponding nitrogen counterpart, 1-azacoumarins also referred to as carbostyrils, are a family of nature-occurring lactones and lactams respectively. The plant extracts containing coumarin-related heterocycles, which were employed as herbal remedies in early days, have now been extensively studied for their biological activities. These investigations have revealed their potentials as versatile biodynamic agents. For example, coumarins with phenolic hydroxyl groups have the ability to scavenge reactive oxygen species and thus prevent the formation of 5-HETE and HHT in the arachidonic pathway of inflammation suppression. Recent in vivo studies have revealed the role of coumarins in hepatotoxicity and also in depletion of cytochrome P450. Similarly 1-azacoumarins which is part of quinoline alkaloids, are known for their diverse biological activity and recently, a 6-functionalized 1-aza coumarins are undergoing human clinical trials as an orally active anti-tumor drug in view of its farnesyl protein-inhibiting activity in the nanomolar range. Furthermore, several synthetic coumarins with a variety of pharmacophoric groups at C-3, C-4 and C-7 positions have been intensively screened for anti-microbial, anti-HIV, anti-cancer, lipid-lowering, anti-oxidant, and anti-coagulation activities. Specifically, coumarin-3-sulfonamides and carboxamides were reported to exhibit selective cytotoxicity against mammalian cancer cell lines. The C4-substituted aryloxymethyl, arylaminomethyl, and dichloroacetamidomethyl coumarins, along with the corresponding 1-azacoumarins, have been demonstrated to be potential anti-microbial and anti-inflammatory agents. To expand the structural diversity of synthetic courmarins for biological functions, attempts have also been made to attach a chloramphenicol side chain at C-3 position of courmarin. In addition, the bi- and tri-heterocyclic coumarins and 1-azacoumarins with benzofuran, furan and thiazole ring systems along with biocompatible fragments like vanillin have shown remarkable potency as anti-inflammatory agents in animal models. Photobiological studies on pyridine-fused polycyclic coumarins have highlighted their potential as thymine dimer photosensitisers and the structurally related compounds of both coumarin and carbostyrils have also been found to act via the DNA gyrase pathway in their anti-bacterial activity. Apart from the above works, the present review also addresses the potential roles of coumarins and carbostyrils as protease inhibitors, or fluorescent probes in mechanistic investigation of biochemical pathways, and their application for QSAR in theoretical studies. Though 1-Azacoumarins have received less attention as compared to coumarins in the literature, an attempt has been made to compare both the systems at various stages, so that it can spark new thoughts on synthetic methodologies, reactivity pattern and biological activities.
香豆素,也被称为苯并吡喃 -2- 酮,以及它们相应的含氮类似物 1-氮杂香豆素(也被称为喹诺酮),分别是一类天然存在的内酯和内酰胺。早期用作草药的含有香豆素相关杂环的植物提取物,如今已因其生物活性而得到广泛研究。这些研究揭示了它们作为多功能生物动力剂的潜力。例如,具有酚羟基的香豆素能够清除活性氧,从而在抑制炎症的花生四烯酸途径中阻止 5-羟基二十碳四烯酸(5-HETE)和 12-羟基-5,8,10,14-二十碳四烯酸(HHT)的形成。最近的体内研究揭示了香豆素在肝毒性以及细胞色素 P450 消耗方面的作用。同样,作为喹啉生物碱一部分的 1-氮杂香豆素,以其多样的生物活性而闻名,最近,鉴于其在纳摩尔范围内的法尼基蛋白抑制活性,一种 6-官能化的 1-氮杂香豆素正在作为口服活性抗肿瘤药物进行人体临床试验。此外,已经对在 C-3、C-4 和 C-7 位具有各种药效基团的几种合成香豆素进行了抗微生物、抗 HIV、抗癌、降脂、抗氧化和抗凝血活性的深入筛选。具体而言,据报道香豆素 -3- 磺酰胺和羧酰胺对哺乳动物癌细胞系表现出选择性细胞毒性。C4-取代的芳氧基甲基、芳氨基甲基和二氯乙酰氨基甲基香豆素,以及相应的 1-氮杂香豆素,已被证明是潜在的抗微生物和抗炎剂。为了扩大合成香豆素用于生物学功能的结构多样性,人们还尝试在香豆素的 C-3 位连接氯霉素侧链。此外,具有苯并呋喃、呋喃和噻唑环系统的双环和三环香豆素以及 1-氮杂香豆素,连同像香草醛这样的生物相容性片段,在动物模型中已显示出作为抗炎剂的显著效力。对吡啶稠合多环香豆素的光生物学研究突出了它们作为胸腺嘧啶二聚体光敏剂的潜力,并且还发现香豆素和喹诺酮的结构相关化合物在其抗菌活性中通过 DNA 回旋酶途径起作用。除了上述工作之外,本综述还讨论了香豆素和喹诺酮作为蛋白酶抑制剂的潜在作用,或在生化途径机理研究中的荧光探针作用,以及它们在理论研究中的定量构效关系(QSAR)应用。尽管与香豆素相比,1-氮杂香豆素在文献中受到的关注较少,但已尝试在各个阶段对这两个体系进行比较,以便能够激发关于合成方法、反应模式和生物活性的新想法。