Phosphinecatalyzed synthesis of highly functionalized coumarins. O o o o o o coumarins are known for their fluorescent properties benzophenone is know for the use in photoaffinity. Review on natural coumarin lead compounds for their. Xanthotoxin is 8methoxy psoralen or 8methoxy 3,26,7 furocoumarin. Coumarins possess a number of biological activities like anticoagulant, antimicrobial. Medicinal chemistry of bioactive natural products wiley. Coumarin enjoys an important place in drug discovery process due to its presence in diversity. Warfarin, the only drug listed here in this category, is a coumarin. Natural and synthetic coumarins as potential anticancer agents. U mbelliferae, r utaceae, l eguminaceae,etc carribean word. Department of pharmaceutical chemistry, delhi pharmaceutical sciences research university, pushp vihar, sec 3, new delhi 110017, india. Chemically, methoxsalen belongs to a class of organic natural molecules known as furanocoumarins. The specific molecular structural features of these four coumarins and the effects on their optoelectronic properties are further examined via a comparison with other similar coumarin derivatives, including coumarins 314, 500, and 522.
Rohini k, srikumar ps 2014 therapeutic role of coumarins and coumarin related compounds. The study of coumarin dates back to 1820 when coumarin was first extracted from tonka bean by vogel. The furan ring can be recognized by using the erlich test. The relationships between the structure and laser dye properties of four coumarin derivatives are investigated to assist in knowledgebased molecular design of coumarins for various optoelectronic applications. Phosphinecatalyzed synthesis of highly functionalized coumarins christopher e. Coumarin3thioformates acting as a new type of 3carbon partner were firstly. The structure and pharmacological functions of coumarins and. Dicoumarol is a mycotoxin, that acts as a blood anticoagulant, is formed during the microbial action of molds and fungi in spoiled hay or silage containing highcoumarin plant. Coumarin belongs to the heterocyclic class of organic compounds, because its molecule contains a ring of atoms of more than one element.
Coumarins have been under extensive studies for their versatile biodynamic activities, for example coumarins with phenolic hydroxyl group have the ability to scavenge reactive oxygen species and thus prevent the formation of 5 hete and 5 hht in arachadonic acid pathway of suppression of inflammation. In this transformation, one new co bond and one new co bond are created. Aug 19, 2005 the medicinal chemistry of ginkgolides from ginkgo biloba recent progress in calophyllum coumarins as potent antihiv agents plantderived antihiv agents and analogs chemical synthesis of annonaceous acetogenins and their structurally modified mimics. Except for a few rare cases, including coumarin itself which is unsubstituted, all plant coumarins contain. Some of its derivatives have been used as aroma enhancers in tobaccos and certain alcoholic drinks 9, 10. New insights into the chemistry and antioxidant activity of coumarins volume. Therefore, the coumarin ring is prevalently applied to construct several functional molecules. Catalysed sequential reaction involving the oxidative ring opening of epoxides by the solvent dmso and an oxa. Another compound imperatorin 2 also shows antiinflammatory activity in.
Coumarins comprise a group of natural compounds found in a variety of plant sources in the form of benzopyrene derivatives. Synthesis of coumarin phenanthridinefused heterocycles and their photochemical and thermochromic properties. A fast and highly efficient green method for synthesizing 3aryl coumarin derivatives from salicylaldehyde and phenyl acetyl chloride in the presence of tetrahydrofuran and k2co3 using ultrasound irradiation is reported. An efficient annulation of phenolic acetates with acrylates in the presence of rh 2 oac 4 as catalyst and formic acid as reducing agent provides high yield of coumarin derivatives via ch bond activation. Coumarins and clickchemistry for photoaffinity labelling. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext.
Coumarins owe their name to coumarin which was the common name for the tonka bean dipteryx odorata, from which the simple compound coumarin was first isolated in 1820. Coumarins an important class of phytochemicals intechopen. Isolation and structural elucidation of novel bioactive. Coumarin 1 exhibits antiinflammatory property and is used in the treatment of oedema. Coumarins are an important class of benzopyrones being the core unit of different natural products and exhibit a spectrum of biological activity. Phosphinecatalyzed synthesis of highly functionalized. Coumarins have not been reported from algae or mosses, although umbelliferone has been reported from a liverwort. New insights into the chemistry and antioxidant activity of. Coumarin has been found in 150 plant species in more. Pdf coumarins an important class of phytochemicals.
Keating gj, okennedy r 1997 the chemistry and occurrence of coumarins. New insights into the chemistry and antioxidant activity of coumarins authors. C 3nsubstituted coumarins can be synthesized in good yields directly from coumarins and azides in the presence of protf 3 without additives or ligands. This removes protein and oedema fluid from injured tissue by stimulating phagocytosis, enzyme production, and thus proteolysis. Coumarins are benzoalphapyrones lactones of ohydroxycinnamic acid formed via the shikimic acid pathway. The coupling of privileged structures results in functionally advantageous compounds. The condensation is performed under acidic conditions. Xanthotoxin is 8 methoxy psoralen or 8methoxy 3,26,7 furocoumarin. Coumarins coumarin 2h1benzopyran2one is a fragrant organic chemical compound in the benzopyrone chemical class, which is a colourless crystalline substance in its standard state. Coumarin scaffold has proven to have an important role in anticancer drug development due to a fact that many of its derivatives have shown an anticancer activity on various cell lines. Coumarins occupy an important place in the realm of natural products and synthetic organic chemistry. Chemical structure of coumarin and the iupac numeration of this scaffold. Some of the industrially important coumarins are the 4methylsubstituted group e.
Coumarins of different kinds are found in many plant species and have widely divergent actions. Coumarins have not been reported from algae or mosses, although. American journal of organic chemistry, 2016 63, pp. Coumarins possess a variety of biological properties, including antimicrobial, antiviral, antiinflammatory, antidiabetic, antioxidant, and enzyme inhibitory activity. Since the discovery of the first coumarin, more than 200 years ago, a huge of number of coumarins and analogues have been either isolated or synthesized. Coumarins have important effects in plant biochemistry and physiology, as they act as antioxidants. Coumarins occupy an important place in the realm of natural products and synthetic organic chemistry1,2.
Their antifungal activity was tested against a panel of 9 clinically relevant strains of yeasts. Coumarins coumarins of different kinds are found in many plant species and have widely divergent actions. Coumarins are 1,2benzopyrones that are derived from the phenylpropanoid pathway. Coumarins coumarin 2hchromen2 one is a fragrant organic chemical compound in the benzopyrone chemical class, which is a colorless crystalline substance in its standard state it is found naturally in many plants families. Coumarin from traditionally used medicinal plant ceropegia juncea roxb. Compounds containing coumarin backbone are a very important group of compounds due to their. Coumarins 1benzopyran2one are chemical compounds in the benzopyrone class of organic compounds found in many plants. The best known and researched coumarins in the field of phytochemistry, pharmacology, medicinal chemistry, and the food science can be found in these families. New insights into the chemistry and antioxidant activity. Coumarins belong to the heterocyclic class of organic compounds, naturally present in a large variety of plant families. Therapeutic role of coumarins and coumarinrelated compounds. Simple coumarins lactones of phenylpropanoic acids with a 2hlbenzopyran2one nucleus are widespread in plants.
They occur widely as secondary plant metabolites and are known to exhibit numerous interesting biological properties. The structure and pharmacological functions of coumarins. Its molecule can be described as a benzene molecule with two adjacent hydrogen atoms replaced by a lactonelike chain. Various coumarins have been prepared via knoevenagel condensation of salicylaldehyde with activated methylene compounds as illustrated in scheme 3. The pechmann reaction 14 is a widely used method for preparing coumarins in. It is an oral anticoagulant that inhibits vitamin k epoxide reductase, an enzyme that that recycles oxidized vitamin k. The journal of organic chemistry 2011, 76 21, 87498755. Ultrasound assisted reactions have resulted in better yields and faster. Coumarins, natural or synthetic, due to their wide range of biological activities, have become an interesting subject of investigation for many researchers. Femtochemistry of hydrogen bonded complexes after electronic.
Except for a few rare cases, including coumarin itself which. Hplc separation and determination of dicoumarol and other. Pdf the coumarin benzopyran2one, or chromen2one ring system, present. Vitamin k is an activator of coagulating factors ii, vii, ix and x, so by decreasing the availability of vitamin k synthesis of these factors are decreased. In the present study, the thirteen new coumarin derivatives are synthesized and characterized by ir and.
Moreira1 1sector of natural products chemistry, universidade estadual do norte fluminense darcy ribeiro, campos dos goytacazes, brazil 2sector of chemistry, instituto federal fluminense, campos dos goytacazes, brazil. Coumarins owe their class name to coumarou, the vernacular name of the tonka bean dipteryx odorata willd, fabaceae, from which coumarin, it was isolated in 1820 bruneton, 1999. Their activities can include antiinflammatory, antispasmodic, antiedematous, and vascular tonic effects. The structure and pharmacological functions of coumarins and their derivatives.
Four coumarins exhibited inhibition of the 5lox pathway and had a similar structure feature containing orthodihydroxyl groups. In nature, coumarins are found in higher plants like rutaceae and umbelliferae and some essential oils like cinnamon bark oil, cassia leaf oil and lavender oil are also rich in coumarins. Now that we know how to identify a coumarin based on its structure, lets talk about how its made synthetically. A regioselective synthesis of naphtho2,1,8def coumarins has been realized through a concise route that involves the intramolecular friedelcrafts reaction of benzof coumarins. There are coumarins as perfumes, cosmetics, and industrial additives. Therefore, these are the coumarins that are going to be further addressed in the next sections of this chapter. Synthesis of polycyclic heteroaromatic coumarins via. The name coumarin comes from a french term for the tonka bean, coumarou, seeds of dipteryx odorata coumarouna odorata fabaceaeleguminosae, one of the sources from which coumarin was first isolated as a natural product in 1820.
Remarkably, changing the solvent from thf to benzene promotes the conversion of the 22nitrostyrenyl allenoate into a tricyclic nitronate through a previously undocumented mode of phosphine catalysis. Coumarins have attracted the attention in recent years because of their diverse pharmacological. Chemistry chemically, methoxsalen belongs to a class of organic natural molecules known as furanocoumarins. Identifiers organic chemistry portal the pechmann condensation is a synthesis of coumarins, starting from a phenol and a carboxylic acid or ester containing a. But their most relevant role is described in natural products, organic chemistry, and medicinal chemistry 11, 12.
Four new crystal structures of coumarins 343, 314t, 445, and 522b are determined at 120 k and analyzed via the empirical harmonicoscillatorstabilizationenergy and bondlength. The sequential reaction allows the rapid and efficient synthesis of 4. The chemistry proceeds via a tandem intermolecular nucleophilic coupling of the nhydroxysuccinimide ester of oacetylsalicylic acid 2 with an. Important examples of the last years have been selected concerning the activities of coumarins as anticoagulant, anticancer, antioxidant, antiviral, antidiabetics. The presence of coumarin in the tonka bean, in which it occurs combined with the sugar glucose, was observed in 1820. Mar 21, 2012 keating gj, okennedy r 1997 the chemistry and occurrence of coumarins.
Tetracyclic, planar products were prepared starting from assembly of the suitably substituted coumarin via the pechmann reaction of 2naphthols with acetone1,3dicarboxylates, followed by an intramolecular friedelcrafts reaction. Synthesis of 3aryl coumarin derivatives using ultrasound. Coumarins form elite classes of naturally occurring compounds, which occupy a special role in nature and interest in its chemistry continues unabated because of its usefulness as biologically active agents. It has a sweet odor, easy to be recognized as the scent of newmown hay. A hplcdad method for determination of coumarins, including dicoumarol, coumarin, and 4. The presence of lactone groups can be observed leading to changes of ph in the medium. This comprehensive reference features articles by some of the worlds leading scientists in the field on discovery, structure elucidation, and elegant synthetic strategiesdeveloped for. Kapdi ar, jain c, padte t, shevde u, pednekar s, et al. In hoults report, sixteen natural and synthetic coumarins were evaluated in rat peritoneal exudate leukocytes for the impact on production of throboxane b 2 and leukotriene b 4. Fulltext html download fulltext pdf 2116 views 1225 downloads. Challenges to obtain pure compounds low concentrations file contains the supporting information of the manuscript rapid synthesis of 4alkynyl coumarins and tunable electronic properties of emission solvatochromic fluorophores, selected 1h and c nmr spectra, uvvis, fluorescence spectra and linear regression analyses of lfer, and dft and tddft computational data. Molecular origins of optoelectronic properties in coumarins. Medicinal chemistry of bioactive natural products provides a muchneeded survey of bioactive natural products and their applications in medicinal chemistry.
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