Coumarin derivatives and their activities.
Abstract
Coumarin (2H-1-benzopyran-2-one) and its heterocyclic derivatives are widely used as lactone scaffolds used by innovative methods for the preparation of heterocyclic molecules. Nowadays, significant biological activities, as well as properties of unique nature coumarin derivatives, have played an important role in the development of novel drugs. This chapter entitles numerous methods of one-pot construction of coumarin derivatives, together with well-known name reactions and other type reactions as well, in the presence of various metal-based homogenous and heterogeneous catalyst system. Coumarin is one of the very important heterocycles and its analogs like natural product and pharmaceutically active drug molecules are extracted/isolated from a plants, animals, and microbes. Coumarin precursors have a wide range of biological activities Hence, the synthesis of coumarins and their heterocyclic analogs have become among the most interesting compound over the last many years in the growth of improved synthetic methodologies to form different types of functional groups that are present in coumarins derivatives. The synthesis of coumarins enabled by current approaches and their most recent bio-applications are discussed in this book chapter. Corresponding complex heterocycles-based coumarin analogs are produced from substituted alkyne substrates and other starting materials as well.
Keywords
- coumarin
- drugs
- catalysis
- name reactions
- arylation
- heterocycles
- radical reaction
1. Introduction
Coumarin heterocycle is an award gifted from nature, coumarins get the name from “Coumarou” which is the vulgarity term of the plant that belongs to the Fabaceae family named tonka bean. The natural product of coumarin and its scaffolds were isolated and purified by Vogel in 1820 [1], and it was prepared by Perkin in 1868 [2]. The lactones-based ubiquitous heterocyclic coumarins have been known as fragrance products in perfumes, because of their nature of sweet smell. Naturally appearing coumarins and their analogs are known in about 700 chemical structures in more than 100 plant families [3] and remarkably, the number of core structures of coumarin derivatives still increases. Coumarins (2
Moreover, coumarins analogs are attracting the vital attention of chemists due to their broad range of materials applications like photosensitizers, fluorescent, optical brighteners [15, 16], and laser dyes [17, 18], and additives [19] in food, cosmetics, and pharmaceuticals, etc.
In this particular lactone based coumarin family of drug molecules such as warfarin [20], acenocoumarol [21], and phenprocoumon [22] are the most prominent ones, which are currently used in a many different nations (Figure 1). Due to their unique nature and greater half-life, notably, warfarin is used more often compare to acenocoumarol. These results highlight a significant new development in the biological evaluation of coumarins and their derivatives, as well as medicinal chemistry [23, 24, 25, 26, 27, 28, 29, 30]. As a current result, the coumarin heterocyclic ring system is widely used mostly in pharmaceutical industry to build a various functional groups present in the drug molecules. Significant research has been shown to isolate and purify naturally present biological active coumarins from a range of plants, animals, and microbes, and to artificially design and synthesize functionalized coumarin molecules from academic and industry as well with unique heterocyclic structures and characteristics [31, 32, 33, 34, 35, 36]. Given the importance of coumarin parent compounds and their derivatives in medicinal chemistry, we have gathered diverse methods for the preparation of coumarin and its scaffolds from alkyne type aryl propiolate as suitable starting materials
2. Name reaction enabled coumarin synthesis
In the present literature, several name reaction mediated methods are reported for the synthesis of coumarin derivatives used by following well-established reaction protocols such as Perkin reaction, Pechmann reaction, Claisen rearrangement, Knoevenagel reaction, Kostanecki-Robinson coupling reaction, Reformatsky Reaction, Wittig reaction, Michael addition, Heck-lactonization reaction, and Baylis–Hillman reaction in the presence of various metal-free or metal-based homogenous and heterogeneous catalyst systems. We have demonstrated suitable reaction and mechanisms for following name reactions mediated preparation of coumarin motifs (Figure 2).
2.1 Perkin reaction
In 1968, the first time Pekin demonstrated the method for the construction of coumarin by the condensation reaction of simple salicylaldehyde in the presence of acetic anhydride [37].
The Perkin reaction of salicylaldehyde
2.2 Pechmann reaction
The Pechmann achieved the initial discovery of the Pechmann condensation in 1883 [39]. Typically, carbolic acid
2.3 Claisen rearrangement
The preparation of 3,4-substituted coumarin utilizing trifluoroacetic acid (TFA) as homogeneous promoter
2.4 Knoevenagel reaction
Many coumarin derivatives have been derived from suitable starting materials
2.5 Kostanecki-Robinson coupling reaction
Kostanecki-Robinson coupling reaction could be utilized for the synthesis of derivatives of coumarin. The Figure 7 shows the reaction between aliphatic anhydride
In 2004 Song et al. synthesized 4-arylcoumarins
2.6 Reformatsky reaction
In the Reformatsky reaction of an activated acyl halide first reacts with a zinc metal to offer RZnBr followed 1,2 addition of organometallic zinc reagents to ketone
2.7 Wittig reaction
Wittig reaction of aldehyde or a ketone
2.8 Michael addition
The synthesis of 3-aroylcoumarin
2.9 Heck-lactonization reaction
The Heck-Lactonization reaction can be carried out for the synthesis of coumarin analogues
2.10 Baylis-Hillman reaction
As seen in Figure 14, the Baylis-Hillman approach was used to create substituted coumarins. In the presence of DABCO, 2-hydroxybenzaldehydes
3. New approaches for the synthesis of coumarins derivatives
3.1 Microwave mediated innovative synthesis
Recently, microwave-mediated organic synthesis has replaced conventional heating methods. In recent years, the synthesis of organic molecules has increasingly relied on the use of microwave energy to heat chemical reactions. In contrast to dramatically accelerating chemical reactions, direct microwave heating is known to reduce the formation of side products, increases yield, and improves the reproducibility. Various academic research institutions have already embraced microwave irradiation as a method for fast reaction in order to efficiently synthesize and discover new chemical substances [54].
In the year 2017, Brahmbatt and co-workers demonstrated the microwave- assisted preparation of 3-aryl-furo[3,2-c] coumarins
In the same year, Desai et al. reported the preparation of 4-(substitutedphenyl)-2-(furan-2-ylmethyleneamino)-6-(2-oxo-2
[3,4-d]triazole-fused coumarin derivatives were synthesized by Schwendt and co-workers. The yield obtained was best (63–94%) in the presence of DMF (solvent) and at 160°C for 1 min [57].
A variety of coumarin-carbonodithioate and coumarin-maltol derivatives were synthesized, showing antibacterial activity and antitumor in a relatively short period in the presence of microwave radiations. It was stated that this approach was 24 times faster than the traditional technology [58, 59].
Pyrido[3,2-c]coumarins were synthesized in the presence of ammonium acetate, the reaction was carried out with suitable starting materials. The yield obtained was good and the time required for the reaction was about 3–4 mins [60]. Synthesis of coumarin-thiazolidine-2,4-dione was carried out recently by Mangasuli and co-workers. The reaction was performed in the presence of K2CO3 (catalyst), the starting material utilized was coumarin and thiazolidinedione.
3.2 Ultrasound helped synthesis
Comparing ultrasonic irradiation to traditional energy sources, there are various benefits like heat, light, and electric potential) [61, 62]. The primary cause of the chemical reactions caused by ultrasound is acoustic cavitation, which is the formation, development, and implosive bursting of bubbles. In many fields of chemistry research, including organic synthesis and solid-state materials, ultrasonic-assisted synthesis techniques have gained a lot of interest as shown Figure 17 [63].
The 3-substituted coumarins
The Pechmann condensation reaction for the synthesis of 3- substituted coumarin
Bis-coumarin derivatives have been synthesized in the presence of ultrasound radiation, the reaction was carried out between various aromatic aldehydes and 4-hydroxycoumarin [66].
3.3 Solvent-free synthesis
Large volumes of hazardous and volatile organic solvents are used in numerous conventional chemical reactions. Green chemistry’s major objective is to replace such toxic reaction solvents. The design of solvent-free green processes has attracted noticeably more interest from researchers as environmental consciousness on a worldwide scale rises. Many researchers have reported the synthesis of coumarin in a solvent free condition. In the year 2014, Sabetpoor et al. reported the synthesis of simple coumarin analogs
The solvent-free Knoevenagel and Pechmann preparation of coumarin
The same authors have also demonstrated the Knovenagel reaction of salicylaldehyde
3.4 Light induced metal-free radical cyclization
In 1912, at the start of the 19th century, Ciamician created a unique technique that used light as a natural source in a chemical reaction. Moreover, utilizing the irradiating method, several organic photochemical processes based on Ultra Violet were developed [70]. In this respect, MacMillan initially investigated in 2008 how a combination of an organocatalyst and a photosensitive catalyst could enhance the asymmetrical alkylation of aldehydes. Because of its unique single electron transfer (SET) path in very mild reaction circumstances, as well as the fact that it is a secure, economical, and sustainable energy source, visible light-irradiated photoredox catalysis has recently gained a lot of interest. By pairing visible light with metals such as Ruthenium, Iridium, Copper, Nickel, and others, many C-C and carbon-heteroatom bonds can be created. Several studies about how to produce coumarins through metal-free/transition-metal catalyzed inter and intramolecular, radical and electrophilic cyclizations have indeed been reported in the literature, but their practical implementation is constrained by the requirement of a toxic metal, substance, or reagent. In order to synthesize coumarins and other compounds, it is crucial to develop simple, practical, and environmentally friendly techniques [71].
A novel photocatalytic technique to produce (3-acyl 4-arylcoumarin)
Li and colleagues described the straightforward photocatalyzed cyclization of alkynoates
Wu and co-workers very recently reported, in 2020, a simple and practical one-pot reaction to synthesize 3-arylacetylene coumarins
3.5 Metal-mediated radical cyclization
Metal-catalyzed reactions have established themselves as one of the crucial steps in the synthesis of organic compounds. There is various methodology reported by chemists for the construction of coumarin derivatives via metal-assisted Radical cyclization reaction. Sulfonyl coumarins
In the year 2018, Zhang et al. reported the synthesis of 3-phenyl sulfonylcoumarins. The reaction is carried out with starting material
Recently in 2019, 3-monofluoromethylated coumarins
3.6 Metal catalyzed electrophilic cyclization
It has been a challenge for chemists and is crucial in the disciplines of agrochemicals, medicines, and healthcare to activate the C-H bond by a metal-catalyst that results in the novel and advantageous chemically synthesized reaction that creates the C-C bond. A beneficial use relates to organic compounds such as annulated arenes, carbocycles, and heterocycles. Intramolecular hydroarylation is the methodical insertion of arene C-H bonds over numerous bonds in an intermolecular approach. In 2014, it was demonstrated that Au(III) catalyzed electrophilic hydroarylation of aryl alkynoate
Anderson and colleagues demonstrated the electrophilic cyclization-catalyzed formation of 3-organoselenyl-2
In 2020, Zaitceva and colleagues showed that cyclometalated (ppy)Pt(II) compounds can catalyze the intramolecular cyclization of phenyl propynoates
3.7 Homogeneous catalytic reaction
In 2014 Chang et al. proposed a gentle and metal-free approach to synthesize 3-sulfenylated coumarins
Wu et al. published a practical and flexible approach for functionalizing 3-sulfenylcoumarin
Later in 2019, Fang and coworkers reported a methodology for the preparation of 3-organoselenyl-2
3.8 Heterogeneous catalytic reaction
One of the foundational elements of the chemical and energy industries is heterogeneous catalysis will play a key role in facilitating the shift to these sectors’ eventual transformation to carbon-neutral operations [83]. Nowadays, heterogenous catalysis is playing an important role in the organic synthesis, and still it is used for converting petroleum as well as natural gas into the cleaner, capable fuels [84, 85].
Researchers have long struggled with the activation of the C-H bond by metal catalysts, which results in the novel and advantageous synthetic organic reaction that creates the C▬C bond and is crucial in the agrochemical, pharmaceutical, and medical fields. Intramolecular hydroarylation, which is the systematic introduction of arene C▬H bonds over multiple bonds in the intermolecular path way, gives a useful organic products like annulated arene carbocycles as well as heterocycles. A novel method has been demonstrated by Yuzo Fujiwara et al. in the year 2000, for the preparation of coumarins and quinolinones
Dalibor and coworkers in 2004 have also demonstrated PtCl4 catalyzed intramolecular electrophilic hydroarylation of various substrates having different structures which includes alkynoate esters
Later in 2004 Chuan and coworkers have described gold(III)-mediated intermolecular hydroarylation reaction of aryl alkynoates
4. Recent applications of coumarin based derivatives
Both natural and synthesized coumarins have received a lot of interest recently due to their various biological and pharmacological characteristics, which expand their industrial potential (Table 1). The usage of coumarins in the creation of biochemical probes has also significantly grown as a result of their photosensitizing and fluorescent capabilities. Umbelliferone, esculetin, and quercetin are coumarins that have anti-oxidant effects and defend against oxidative damage to cellular DNA [89, 90]. Esculetin has been reported best for protecting cells from oxidative damages [91]. By preventing vitamin K from working, the dicumarol exhibits anti-coagulant qualities, whereas angelmarin has been utilized for pancreatic cancer. Sakaguchi and co-workers reported numerous derivatives of coumarin, including 7,7-dihydroxy-coumarins and others, which are known to have anti-oxidant effects. Free radical production results in oxidative damage to DNA, which activates p53. Recently, in 2017 and 2018, Sahu [92] and co-workers and Witaicenis [93] and coworkers respectively, reported the antioxidant property of 4-methylesculetin. Coumarin structures like Cloricromene, Warfarin shows good anti-cancer activity and there are being used in the treatment of cancer. Vipirinin, a derivative of coumarin has is used to suppress the Vpr-depended gene (viral) and thus acts as an antagonist [94]. Osthol, a coumarin is well known for its antioxidant property which prevents acetaminophen activation as well as functions in the regulation of the concentration of free calcium that exists in the intracellular space [95]. Coumarins’ photosensitivity is beneficial for detecting the activation of particular enzymes as well as bio-molecules including DNA, protein, as well as lipids [96]. Also, they have been utilized in the area of pharmacology to analyze the potency of various drug molecules. Furanocoumarins acts as potent photo-sensitizing agents by killing bacteria and inactivating virus in a conjugated reaction with Ultraviolet light (Figure 38) [13].
S. No. | Activity | Derivative of coumarin | Reference |
---|---|---|---|
1 | Antioxidant [97, 98, 99] | Chrysin Scopoletin Umbelliferone | [97, 98, 99] |
2 | Antiinflammatory [100, 101, 102] | Esculetin 4-methyl esculetin Umbelliferone-6-carboxylic acid Scopoletin | [100, 101, 102] |
3 | Anticancer [103, 104, 105, 106, 107] | Esculetin Umbelliferone Scopoletin Cloricromene | [103, 104, 105, 106] |
4 | Anticoagulant [22, 108, 109] | Warfarin Acenocoumarol | [22, 108, 109] |
5 | Photosensitivity [110, 111] | Furanocoumarins Psoralens | [110, 111] |
6 | Enzyme inhibitors [105, 112] | Daphnetin Vipirinin | [105, 112] |
5. Conclusions
Coumarin derivatives are highly valuable lactone-based organic molecules for academics and bio-pharma industries due to the unique nature of chemical properties, and flexible design system to access a broad range of functionalized coumarin scaffolds via simple synthetic chemical transformation as a result, a huge number of coumarin derivatives have been successfully developed and produced in single steps. This review permits many protocols of one-pot construction of coumarins and their derivatives, together with well-studied name reactions and other types of coupling reactions as well using different metal-based catalysis, and visible light-mediated photocatalysis. While these aforementioned traditional name reactions have been employed for several decades, new methods developments have been widely achieved in the last few years such as microwave-, ultrasound-helped, light-induced metal-free radical cyclization, metal-mediated radical cyclization, metal-catalyzed electrophilic cyclization, miscellaneous, homogeneous catalytic reaction and heterogeneous catalytic reaction and solvent-free conditions, This new system were applied in a challenge to maximize the single-pot reaction yield, diminish the reaction time, and reduce the unwanted side reactions and as well as making these reactions more bioactive candidates. This review concluded that this catalysis-based new developments can play an increasing role in the preparation of highly substituted coumarin derivatives by modifying the unpleasant typical reaction conditions associated with the standard synthetic routes.
Acknowledgments
The authors acknowledge ICT-IOC, Bhubaneswar for providing necessary support. Rambabu Dandela thanks DST-SERB for Ramanujan fellowship (SB/S2/RJN-075/2016), Core research grant (CRG/2018/000782) and ICT-IOC start-up grant, Mahender Khatravath thanks Central University of South Bihar, for providing the facilities. Vasudevan Dhayalan expresses his gratitude to the DST-SERB for the Ramanujan Fellowship (Grant No. RJF/2020/000038) and the National Institute of Technology Puducherry, Karaikal, India for their assistance with research.
Notes/thanks/other declarations
VD and CM Thanks to SERB for the Ramanujan Fellowship and NIT-Puducherry.
References
- 1.
Matos MJ, Santana L, Uriarte E, Abreu OA, Molina E, Yordi EG. Coumarins — An Important Class of Phytochemicals. In: Rao AV, Rao LG, editors. Phytochemicals - Isolation, Characterisation and Role in Human Health. IntechOpen. 2015:113-140. DOI: 10.5772/59982 - 2.
Perkin WH. On the hydride of aceto-salicyl. Journal of the Chemical Society. 1868; 21 :181-186. DOI: 10.1039/JS8682100181 - 3.
Jain PK, Joshi H. Coumarin: Chemical and pharmacological profile. Journal of Applied Pharmaceutical Science. 2012; 2 (6):236-240. DOI: 10.7324/JAPS.2012.2643 - 4.
Santana L, Uriarte E, Roleira F, Milhazes N, Borges F. Furocoumarins in medicinal chemistry. Synthesis, natural occurrence and biological activity. Current Medicinal Chemistry. 2012; 11 (24):3239-3261. DOI: 10.2174/0929867043363721 - 5.
Signore G, Nifosì R, Albertazzi L, Storti B, Bizzarri R. Polarity-sensitive coumarins tailored to live cell imaging. Journal American Chemical Society. 2010; 132 (4):1276-1288. DOI: 10.1021/ja9050444 - 6.
Balewski Ł, Szulta S, Jalińska A, Kornicka A. A mini-review: Recent advances in coumarin-metal complexes with biological properties. Frontiers in Chemistry. 2021; 9 :1-18. DOI: 10.3389/fchem.2021.781779 - 7.
Nasab NH, Azimian F, Kruger HG, Kim SJ. Coumarin-chalcones generated from 3-acetylcoumarin as a promising agent: Synthesis and pharmacological properties. Chemistry Select. 2022; 7 (11):1-13. DOI: 10.1002/slct.202200238 - 8.
Nakamura Y, Sakata Y, Hosoya T, Yoshida S. Synthesis of functionalized benzopyran/coumarin-derived aryne precursors and their applications. Organic Letter. 2020; 22 (21):8505-8510. DOI: 10.1021/acs.orglett.0c03106 - 9.
Zhao YR, Zheng Q, Dakin K, Xu K, Martinez ML, Li WH. New caged coumarin fluorophores with extraordinary uncaging cross sections suitable for biological imaging applications. Journal of American Chemistry Society. 2004; 126 (14):4653-4663. DOI: 10.1021/ja036958m - 10.
Kulkarni M, Kulkarni G, Lin C-H, Sun C-M. Recent advances in coumarins and 1-azacoumarins as versatile biodynamic agents. Current Medicinal Chemistry. 2006; 13 (23):2795-2818. DOI: 10.2174/092986706778521968 - 11.
Prahadeesh N, Sithambaresan M, Mathiventhan U. A study on hydrogen peroxide scavenging activity and ferric reducing ability of simple coumarins. Emerging Science Journal. 2018; 2 (6):417-427. DOI: 10.28991/esj-2018-01161 - 12.
Bhatnagar A, Sharma PK, Kumar N, Dhudhe RA. Review on recent advances in coumarin derivatives with their multidisciplinary actions. Der Pharmacia Lettre. 2010; 2 (4):297-306 - 13.
Sandhu S, Bansal Y, Silakari O, Bansal G. Coumarin hybrids as novel therapeutic agents. Bioorganic Medicinal Chemistry. 2014; 22 (15):3806-3814. DOI: 10.1016/j.bmc.2014.05.032 - 14.
Calcio Gaudino E, Tagliapietra S, Martina K, Palmisano G, Cravotto G. Recent advances and perspectives in the synthesis of bioactive coumarins. Royal Society of Chemistry Advance. 2016; 6 (52):46394-46405. DOI: 10.1039/c6ra07071j - 15.
Abdallah M, Hijazi A, Dumur F, Lalevée J. Coumarins as powerful photosensitizers for the cationic polymerization of epoxy-silicones under near-UV and visible light and applications for 3D printing technology. Molecules. 2020; 25 (9):1-12. DOI: 10.3390/molecules25092063 - 16.
Zhang G, Zheng H, Guo M, Du L, Liu G, Wang P. Synthesis of polymeric fluorescent brightener based on coumarin and its performances on paper as light stabilizer, fluorescent brightener and surface sizing agent. Applied Surface Science. 2016; 367 :167-173. DOI: 10.1016/j.apsusc.2016.01.110 - 17.
Bakhtiari G, Moradi S, Soltanali S. A novel method for the synthesis of coumarin laser dyes derived from 3-(1H-Benzoimidazol-2-Yl) coumarin-2-one under microwave irradiation. Arabian. Journal of Chemistry. 2014; 7 (6):972-975. DOI: 10.1016/j.arabjc.2010.12.012 - 18.
Liu X, Cole JM, Waddell PG, Lin TC, Radia J, Zeidler A. Molecular origins of optoelectronic properties in coumarin dyes: Toward designer solar cell and laser applications. Journal of Physical Chemistry. 2012; 116 (1):727-737. DOI: 10.1021/jp209925y - 19.
Chen T, Ma L, Tang Z, Yu LX. Identification of coumarin-based food additives using terahertz spectroscopy combined with manifold learning and improved support vector machine. Journal of Science. 2022; 87 (3):1108-1118. DOI: 10.1111/1750-3841.16064 - 20.
Wong TC, Sultana CM, Vosburg DA. A green, enantioselective synthesis of warfarin for the undergraduate organic laboratory. Journal of Chemical Education. 2010; 87 (2):194-195. DOI: 10.1021/ed800040m - 21.
Bipat R. From rat poison to medicine: Medical applications of coumarin derivatives. Phytochemicals in Human Health. 2020:1-14. DOI: 10.5772/intechopen.89765 - 22.
Verhoef TI, Redekop WK, Daly AK, Van Schie RMF, De Boer A, Maitland-Van Der Zee AH. Pharmacogenetic-guided dosing of coumarin anticoagulants: Algorithms for Warfarin, acenocoumarol and phenprocoumon. British Journal of Clinical Pharmacology. 2014; 77 (4):626-641. DOI: 10.1111/bcp.12220 - 23.
Rastij V, Vrandečić K, Ćosić J, Šarić GK, Majić I, Agić D, et al. Effects of coumarinyl schiff bases against phytopathogenic fungi, the soil-beneficial bacteria and entomopathogenic nematodes: Deeper insight into the mechanism of action. Molecules. 2022; 27 (7):1-17. DOI: 10.3390/molecules27072196 - 24.
Choi TJ, Song J, Park HJ, Kang SS, Lee SK. Anti-Inflammatory activity of glabralactone, a coumarin compound from angelica sinensis, via suppression of TRIF-Dependent IRF-3 signaling and NF- κ B pathways. Mediators of Inflammation. 2022; 2022 :1-11. DOI: 10.1155/2022/5985255 - 25.
Rawat A, Vijaya Bhaskar Reddy A. Recent advances on anticancer activity of coumarin derivatives. European Journal Medicinal Chemistry Reports. 2022; 5 :100038. DOI: 10.1016/j.ejmcr.2022.100038 - 26.
Metwally NH, Elgemeie GH, Fahmy FG. Green synthesis: Antimicrobial activity of novel benzothiazole-bearing coumarin derivatives and their fluorescence properties. Egyptian Journal of Chemistry. 2022; 65 (2):679-686. DOI: 10.21608/EJCHEM.2021.91887.4365 - 27.
Dianhar H, Tristiyana QR, Purba AWA, Handayani S, Sugita P, Rahayu DUC. Antibacterial activities of 3-substituted coumarin-scaffolds synthesized under microwave irradiation. Journal Hunan University Natural Science. 2022; 49 (1):38-46. DOI: 10.55463/issn.1674-2974.49.1.6 - 28.
Patil SM, Martiz RM, Satish AM, Shbeer AM, Ageel M, Al-Ghorbani M, et al. Discovery of novel coumarin derivatives as potential dual inhibitors against α-glucosidase and α-amylase for the management of post-prandial hyperglycemia via molecular modelling approaches. Molecules. 2022; 27 (12):1-38. DOI: 10.3390/molecules27123888 - 29.
Musa MA, Cooperwood JS, Khan MO. A review of coumarin derivatives in pharmacotherapy of breast cancer. Current Medicinal Chemistry. 2008; 15 (26):2664-2679. DOI: 10.2174/092986708786242877 - 30.
Tejedor D, Delgado-Hernandez S, Diana-Rivero R, Diaz-Diaz A, Garcia-Tellado F. Recent advances in the synthesis of 2H-Pyrans. Molecules. 2019; 24 (16):2119-2132. DOI: 10.3390/molecules24162904 - 31.
Venugopala KN, Rashmi V, Odhav B. Review on natural coumarin lead compounds for their pharmacological activity. Biomed Research International. 2013:1-14. DOI: 10.1155/2013/963248 - 32.
Sharma D, Dhayalan V, Chatterjee R, Khatravath M, Dandela R. Recent advances in the synthesis of coumarin and its derivatives by using aryl propiolates. Chemistry Select. 2022; 7 (4):1-25. DOI: 10.1002/slct.202104299 - 33.
Cao D, Liu Z, Verwilst P, Koo S, Jangjili P, Kim JS, et al. Coumarin-based small-molecule fluorescent chemosensors. Chemical Reviews. 2019; 119 (18):10403-10519. DOI: 10.1021/acs.chemrev.9b00145 - 34.
Dreyer DL, Jones KC, Jurd L, Campbell BC. Feeding deterrency of some 4-hydroxycoumarins and related compounds: Relationship to host-plant resistance of alfalfa towards pea aphid (acyrthosiphon pisum). Journal of Chemical Ecology. 1987; 13 (4):925-930. DOI: 10.1007/BF01020171 - 35.
Ganeshapillai D, Woo LWL, Thomas MP, Purohit A, Potter BVL. C-3- and C-4-substituted bicyclic coumarin sulfamates as potent steroid sulfatase inhibitors. ACS Omega. 2018; 3 (9):10748-10772. DOI: 10.1021/acsomega.8b01383 - 36.
Bozdag M, Alafeefy AM, Altamimi AM, Vullo D, Carta F, Supuran CT. Coumarins and other fused bicyclic heterocycles with selective tumor-associated carbonic anhydrase isoforms inhibitory activity. Bioorganic Medicinal Chemistry. 2017; 25 (2):677-683. DOI: 10.1016/j.bmc.2016.11.039 - 37.
Rabbani GA. Concise introduction of perkin reaction. Organic Chemistry: Current Research. 2018; 07 (02):7-10. DOI: 10.4172/2161-0401.1000191 - 38.
Buckles RE. The use of the perkin reaction in organic laboratory classes. Journal of Chemical Education. 1950; 27 (4):210-211. DOI: 10.1021/ed027p210 - 39.
Lončarić M, Sokač DG, Jokić S, Molnar M. Recent advances in the synthesis of coumarin derivatives from different starting materials. Biomolecules. 2020; 10 (1):1-36. DOI: 10.3390/biom10010151 - 40.
Zambare AS, Kalam Khan FA, Zambare SP, Shinde SD, Sangshetti JN. Recent advances in the synthesis of coumarin derivatives via pechmann condensation. Current Organic Chemistry. 2015; 20 (7):798-828. DOI: 10.2174/1385272820666151026224227 - 41.
Gulati S, Singh R, Sangwan S. A review on convenient synthesis of substituted coumarins using reuseable solid acid catalysts. Royal Society of Chemistry Advances. 2021; 11 (47):29130-29155. DOI: 10.1039/d1ra04887b - 42.
Chavan SP, Shivasankar K, Sivappa R, Kale R. Zinc mediated transesterification of β-ketoesters and coumarin synthesis. Tetrahedron Letter. 2002; 43 (47):8583-8586. DOI: 10.1016/S0040-4039(02)02006-3 - 43.
Mustafa YF. Classical approaches and their creative advances in the synthesis of coumarins: A brief review. Journal of Medicinal Chemistry. 2021; 4 (6):612-625. DOI: 10.26655/JMCHEMSCI.2021.6.10 - 44.
Valizadeh H, Gholipour H. Imidazolium-based phosphinite ionic liquid (IL-OPPh2) as reusable catalyst and solvent for the knoevenagel condensation reaction. Synthetic Communication. 2010; 40 (10):1477-1485. DOI: 10.1080/00397910903097310 - 45.
Sripathi SK, Logeeswari K. Synthesis of 3-aryl coumarin derivatives using ultrasound. International Journal of Organic Chemistry. 2013; 03 (01):42-47. DOI: 10.4236/ijoc.2013.31004 - 46.
Gholap SS, Deshmukh UP, Tambe MS. Synthesis and in-vitro antimicrobial screening of 3-cinnamoyl coumarin and 3-[3-(1H-Indol-2-Yl)-3-Aryl-Propanoyl]-2H-Chromen-2-Ones. Iranian Journal of Catalysis. 2013; 3 (3):171-176 - 47.
Hwang IT, Lee SA, Hwang JS, Lee KI. A facile synthesis of highly functionalized 4-arylcoumarins via kostanecki reactions mediated by DBU. Molecules. 2011; 16 (8):6313-6321. DOI: 10.3390/molecules16086313 - 48.
Song CE, Jung DU, Choung SY, Roh EJ, Lee SG. Dramatic enhancement of catalytic activity in an ionic liquid: Highly practical friedel-crafts alkenylation of arenes with alkynes catalyzed by metal triflates. Angewandte Chemie - Inernational Edition. 2004; 43 (45):6183-6185. DOI: 10.1002/anie.200460292 - 49.
Hintermann L. Comprehensive organic name reactions and reagents. By Zerong Wang. Angewandte Chemie - Inernational Edition. 2010; 49 (15):2659-2660. DOI: 10.1002/anie.201000292 - 50.
Upadhyay PK, Kumar PA. Novel synthesis of coumarins employing triphenyl(α-carboxymethylene)phosphorane imidazolide as a C-2 synthon. Tetrahedron Letter. 2009; 50 (2):236-238. DOI: 10.1016/j.tetlet.2008.10.133 - 51.
Rao HSP, Sivakumar S. Condensation of α-aroylketene dithioacetals and 2- hydroxyarylaldehydes results in facile synthesis of a combinatorial library of 3-aroylcoumarins. Journal of Organic Chemistry. 2006; 71 (23):8715-8723. DOI: 10.1021/jo061372e - 52.
Fernandes TDA, Gontijo Vaz B, Eberlin MN, Da Silva AJM, Costa PRR. Palladium-catalyzed tandem heck-lactonization from o-iodophenols and enoates: Synthesis of coumarins and the study of the mechanism by electrospray ionization mass spectrometry. The Journal of Organic Chemistry. 2010; 75 (21):7085-7091. DOI: 10.1021/jo1010922 - 53.
Kaye PT, Robinson RS. Dabco-catalysed reactions of salicylaldehydes with acrylate derivatives. Synthetic Communication. 1996; 26 (11):2085-2097. DOI: 10.1080/00397919608003567 - 54.
Nüchter M, Ondruschka B, Bonrath W, Gum A. Microwave assisted synthesis – A critical technology overview. Green Chemistry. 2004; 6 (3):128-141. DOI: 10.1039/b310502d - 55.
Kaneria AR, Giri RR, Bhila VG, Prajapati HJ, Brahmbhatt DI. Microwave assisted synthesis and biological activity of 3-Aryl-Furo[3,2-c]Coumarins. Arabian Journal of Chemistry. 2017; 10 :S1100-S1104. DOI: 10.1016/j.arabjc.2013.01.017 - 56.
Desai NC, Satodiya HM, Rajpara KM, Joshi VV, Vaghani HV. A microwave-assisted facile synthesis of novel coumarin derivatives containing cyanopyridine and furan as antimicrobial agents. Journal of Saudi Chemical Society. 2017; 21 :S153-S162. DOI: 10.1016/j.jscs.2013.12.005 - 57.
Schwendt G, Glasnov T. Intensified synthesis of [3,4-d]triazole-fused chromenes, coumarins, and quinolones. Monatshefte fur Chemie. 2017; 148 (1):69-75. DOI: 10.1007/s00706-016-1885-5 - 58.
Mangasuli SN, Hosamani KM, Satapute P, Joshi SD. Synthesis, molecular docking studies and biological evaluation of potent coumarin–Carbonodithioate hybrids via microwave irradiation. Chemical Data Collection. 2018; 15–16 :115-125. DOI: 10.1016/j.cdc.2018.04.001 - 59.
Koparde S, Hosamani KM, Barretto DA, Joshi SD. Microwave synthesis of coumarin-maltol hybrids as potent antitumor and anti-microbial drugs: An approach to molecular docking and DNA cleavage studies. Chemical Data Collection. 2018; 15–16 :41-53. DOI: 10.1016/j.cdc.2018.03.004 - 60.
Kolita S, Bhuyan PJ. An efficient synthesis of pyrido[3, 2-c]coumarins under microwave irradiation in solvent-free conditions. Chemistry Select. 2018; 3 (5):1411-1414. DOI: 10.1002/slct.201702957 - 61.
Kaur N. Ultrasound-assisted green synthesis of five-membered O- and S-Heterocycles. Synthetic Communication. 2018; 48 (14):1715-1738. DOI: 10.1080/00397911.2018.1460671 - 62.
Banerjee B. Recent developments on ultrasound assisted catalyst-free organic synthesis. Ultrasonics Sonochemistry. 2017; 35 :1-14. DOI: 10.1016/j.ultsonch.2016.09.023 - 63.
Liu Y, Myers EJ, Rydahl SA, Wang X. Ultrasonic-assisted synthesis, characterization, and application of a metal-organic Framework: A green general chemistry laboratory project. Journal of Chemical Education. 2019; 96 (10):2286-2291. DOI: 10.1021/acs.jchemed.9b00267 - 64.
Ghomi JS, Akbarzadeh Z. Ultrasonic accelerated knoevenagel condensation by magnetically recoverable MgFe2O4 nanocatalyst: A rapid and green synthesis of coumarins under solvent-free conditions. Ultrasonics Sonochemistry. 2018; 40 :78-83. DOI: 10.1016/j.ultsonch.2017.06.022 - 65.
Prousis KC, Avlonitis N, Heropoulos GA, Calogeropoulou T. FeCl3-Catalysed ultrasonic-assisted, solvent-free synthesis of 4-substituted coumarins. A useful complement to the pechmann reaction. Ultrasonics Sonochemistry. 2014; 21 (3):937-942. DOI: 10.1016/j.ultsonch.2013.10.018 - 66.
Al-Kadasi AMA, Nazeruddi GM. Ultrasound assisted catalyst-free one -pot synthesis of Bis-Coumarins in neat water. International Journal of Chemical Science. 2012; 10 (1):324-330 - 67.
Sabetpoor S, Hatamjafari F. Synthesis of coumarin derivatives using glutamic acid under solvent-free conditions. Oriental Journal of Chemistry. 2014; 30 (2):863-865. DOI: 10.13005/ojc/300265 - 68.
Sugino T, Tanaka K. Solvent-free coumarin synthesis. Chemistry Letters. 2001; 2 :110-111. DOI: 10.1246/cl.2001.110 - 69.
Sharma D, Kumar S, Makrandi JK. Modified pechmann condensation using grinding technique under solvent-free condition at roomtemperature. Green Chemistry Letters and Reviews. 2011; 4 (2):127-129. DOI: 10.1080/17518253.2010.517785 - 70.
Ciamician G. The Photochemistry of the future. Science. 1912; 36 (926):385-394. DOI: 10.1126/science.36.926.385 - 71.
Wang Z, Li X, Wang L, Li P. Photoinduced cyclization of alkynoates to coumarins with n-iodosuccinimide as a free-radical initiator under ambient and metal-free conditions. Tetrahedron. 2019; 75 (8):1044-1051. DOI: 10.1016/j.tet.2019.01.013 - 72.
Kawaai K, Yamaguchi T, Yamaguchi E, Endo S, Tada N, Ikari A, et al. Photoinduced generation of acyl radicals from simple aldehydes, access to 3-Acyl-4-arylcoumarin derivatives, and evaluation of their antiandrogenic activities. Journal of Organic Chemistry. 2018; 83 (4):1988-1996. DOI: 10.1021/acs.joc.7b02933 - 73.
Wu X, Jia M, Huang M, Kim JK, Zhao Z, Liu J, et al. A visible-light-induced “on-off” one-pot synthesis of 3-arylacetylene coumarins with AIE Properties. Organic and Biomolecular Chemistry. 2020; 18 (17):3346-3353. DOI: 10.1039/d0ob00479k - 74.
Kanyiva KS, Hamada D, Makino S, Takano H, Shibata T. α-Amino acid sulfonamides as versatile sulfonylation reagents: Silver-catalyzed synthesis of coumarins and oxindoles by radical cyclization. European Journal of Organic Chemistry. 2018; 2018 (43):5905-5909. DOI: 10.1002/ejoc.201800901 - 75.
Ren H, Mu Y, Zhang M, Zhang AQ. Synthesis of 3-phenylsulfonylcoumarins by cyclisation of phenyl propiolates with sulfinic acids or sodium sulfinates. Journal of Chemical Research. 2018; 42 (10):515-520. DOI: 10.3184/174751918X15385227785338 - 76.
Fu W, Sun Y, Li X. Silver-catalyzed monofluoromethylation of alkynoates with sodium monofluoroalkanesulfinate (CH2FSO2Na) to Access 3-monofluoromethylated coumarins. Synthetic. Communication. 2020; 50 (3):388-398. DOI: 10.1080/00397911.2019.1697452 - 77.
Aparece MD, Vadola PA. Gold-catalyzed dearomative spirocyclization of aryl alkynoate esters. Organic Letter. 2014; 16 (22):6008-6011. DOI: 10.1021/ol503022h - 78.
Mantovani AC, Goulart TAC, Back DF, Menezes PH, Zeni G. Iron(III) chloride and diorganyl diselenides-mediated 6- endo-dig cyclization of Arylpropiolates and Arylpropiolamides leading to 3-organoselenyl-2 h -Coumarins and 3-Organoselenyl-Quinolinones. Journal of Organic Chemistry. 2014; 79 (21):10526-10536. DOI: 10.1021/jo502199q - 79.
Zaitceva O, Bénéteau V, Ryabukhin DS, Eliseev II, Kinzhalov MA, Louis B, et al. Cyclization of aryl 3-aryl propynoates into 4-arylcoumarins catalyzed by cyclometalated platinum(II) complexes. Tetrahedron. 2020; 76 (14):1-9. DOI: 10.1016/j.tet.2020.131029 - 80.
Gao WC, Liu T, Zhang B, Li X, Wei WL, Liu Q, et al. Synthesis of 3-sulfenylated coumarins: BF3·Et2O-mediated electrophilic cyclization of aryl alkynoates using N-sulfanylsuccinimides. Journal of Organic Chemistry. 2016; 81 (22):11297-11304. DOI: 10.1021/acs.joc.6b02271 - 81.
Wu W, An Y, Li J, Yang S, Zhu Z, Jiang H. Iodine-catalyzed cascade annulation of alkynes with sodium arylsulfinates: Assembly of 3-sulfenylcoumarin and 3-sulfenylquinolinone derivatives. Organic Chemistry Frontiers. 2017; 4 (9):1751-1756. DOI: 10.1039/c7qo00326a - 82.
Fang JD, Yan XB, Zhou L, Wang YZ, Liu XY. Synthesis of 3-organoselenyl-2H-coumarins from propargylic aryl ethers via oxidative radical cyclization. Advanced Synthesis and Catalysis. 2019; 361 (9):1985-1990. DOI: 10.1002/adsc.201801565 - 83.
Friend CM, Xu B. Heterogeneous catalysis: A central science for a sustainable future. Accounts of Chemical Research. 2017; 50 (3):517-521. DOI: 10.1021/acs.accounts.6b00510 - 84.
Descorme C, Gallezot P, Geantet C, George C. Heterogeneous catalysis: A key tool toward sustainability. ChemCatChem. 2012; 4 (12):1897-1906. DOI: 10.1002/cctc.201200483 - 85.
Maheswara M, Siddaiah V, Damu GLV, Rao YK, Rao CV. A Solvent-free synthesis of coumarins via pechmann condensation using heterogeneous catalyst. Journal of Molecular Catalysis A: Chemical. 2006; 255 :49-52. DOI: 10.1016/j.molcata.2006.03.051 - 86.
Jia C, Piao D, Kitamura T, Fujiwara Y. New method for preparation of coumarins and quinolinones via Pd-catalyzed intramolecular hydroarylation of C-C triple bonds. Journal of Organic Chemistry. 2000; 65 (22):7516-7522. DOI: 10.1021/jo000861q - 87.
Pastine SJ, Youn SW, Sames D. PtIV-catalyzed cyclization of arene-alkyne substrates via intramolecular electrophilic hydroarylation. Organic Letter. 2003; 5 (7):1055-1058. DOI: 10.1021/ol034177k - 88.
Shi Z, He C. Efficient functionalization of aromatic C-H bonds catalyzed by Gold(III) under mild and solvent-free conditions. Journal of Organic Chemistry. 2004; 69 (11):3669-3671. DOI: 10.1021/jo0497353 - 89.
Garg SS, Gupta J, Sharma S, Sahu D. An insight into the therapeutic applications of coumarin compounds and their mechanisms of action. European Journal of Pharmaceutical Sciences. 2020; 152 :105424. DOI: 10.1016/j.ejps.2020.105424 - 90.
Ren QC, Gao C, Xu Z, Feng LS, Liu ML, Wu X, et al. Bis-coumarin derivatives and their biological activities. Current Topics in Medicinal Chemistry. 2018; 18 (2):101-113. DOI: 10.2174/1568026618666180221114515 - 91.
Liang C, Ju W, Pei S, Tang Y, Xiao Y. Pharmacological activities and synthesis of esculetin and its derivatives: A mini-review. Journal of Lipid Research. 2017; 58 (3):519-528. DOI: 10.3390/molecules22030387 - 92.
Sahu D, Sharma S, Singla RK, Panda AK. Antioxidant activity and protective effect of suramin against oxidative stress in collagen induced arthritis. European Journal of Pharmaceutical Sciences. 2017; 101 :125-139. DOI: 10.1016/j.ejps.2017.02.013 - 93.
Witaicenis A, de Oliveira ECS, Tanimoto A, Zorzella-Pezavento SFG, de Oliveira SL, Sartori A, et al. 4-Methylesculetin, a coumarin derivative, ameliorates dextran sulfate sodium-induced intestinal inflammation. Chemical Biological Interactions. 2018; 280 :59-63. DOI: 10.1016/j.cbi.2017.12.006 - 94.
Ong EBB, Watanabe N, Saito A, Futamura Y, Abd El Galil KH, Koito A, et al. Vipirinin, a coumarin-based HIV-1 Vpr inhibitor, interacts with a hydrophobic region of Vpr. Journal of Biological Chemistry. 2011; 286 (16):14049-14056. DOI: 10.1074/jbc.M110.185397 - 95.
Cai Y, Sun W, Zhang XX, Lin YD, Chen H, Li H. Osthole prevents acetaminophen-induced liver injury in mice. Acta Pharmaceutica Sinica B. 2018; 39 (1):74-84. DOI: 10.1038/aps.2017.129 - 96.
Deasy B, Bogan DP, Smyth MR, O'Kennedy R, Fuhr U. Study of coumarin metabolism by human liver microsomes using capillary electrophoresis. Analytica Chimica Acta. 1995; 310 (1):101-107. DOI: 10.1016/0003-2670(95)00136-N - 97.
Pushpavalli G, Kalaiarasi P, Veeramani C, Pugalendi KV. Effect of chrysin on hepatoprotective and antioxidant status in D-galactosamine-induced hepatitis in rats. European. Journal of Pharmacology. 2010; 631 :36-41. DOI: 10.1016/j.ejphar.2009.12.031 - 98.
Shaw CY, Chen CH, Hsu CC, Chen CC, Tsai YC. Antioxidant properties of scopoletin isolated from sinomonium acutum. Phythotherapy Research. 2003; 17 (7):823-825. DOI: 10.1002/ptr.1170 - 99.
Luzi F, Puglia D, Dominici F, Fortunati E, Giovanale G, Balestra GM, et al. Effect of gallic acid and umbelliferone on thermal, mechanical, antioxidant and antimicrobial properties of poly (vinyl alcohol-co-ethylene) films. Polymer Degradation and Stability. 2018; 152 :162-176. DOI: 10.1016/j.polymdegradstab. 2018.04.015 - 100.
Witaicenis A, Seito LN, Di Stasi LC. Intestinal anti-inflammatory activity of esculetin and 4-methylesculetin in the trinitrobenzenesulphonic acid model of rat colitis. Chemical Biological Interaction. 2010; 186 (2):211-218. DOI: 10.1016/j.cbi.2010.03.045 - 101.
Nurul Islam M, Joo Choi R, Eun Jin S, Shik Kim Y, Ra Ahn B, Zhao D, et al. Mechanism of anti-inflammatory activity of umbelliferone 6-carboxylic acid isolated from angelica decursiva. Journal of Ethnopharmacology. 2012; 144 (1):175-181. DOI: 10.1016/j.jep.2012.08.048 - 102.
Ding Z, Dai Y, Hao H, Pan R, Yao X, Wang Z. Anti-inflammatory effects of scopoletin and underlying mechanisms. Pharmaceutical Biology. 2008; 46 (12):854-860. DOI: 10.1080/13880200802367155 - 103.
Turkekul K, Colpan RD, Baykul T, Ozdemir MD, Erdogan S. Esculetin inhibits the survival of human prostate cancer cells by inducing apoptosis and arresting the cell cycle. Journal of Cancer Prevention. 2018; 23 (1):10-17. DOI: 10.15430/jcp.2018.23.1.10 - 104.
Chu LL, Pandey RP, Lim HN, Jung HJ, Thuan NH, Kim TS, et al. Synthesis of umbelliferone derivatives in escherichia coli and their biological activities. Journal of Biological Engineering. 2017; 11 (1):1-11. DOI: 10.1186/s13036-017-0056-5 - 105.
Liang SC, Ge GB, Xia YL, Pei-Pei D, Ping W, Qi XY, et al. Inhibition of human catechol-O-methyltransferase-mediated dopamine O-methylation by daphnetin and its phase II metabolites. Xenobiotica. 2017; 47 (6):498-504. DOI: 10.1080/00498254.2016.1204567 - 106.
Shi X, Li H, Shi A, Yao H, Ke K, Dong C, et al. Discovery of rafoxanide as a dual CDK4/6 inhibitor for the treatment of skin cancer. Oncology Reports. 2018; 40 (3):1592-1600. DOI: 10.3892/or.2018.6533 - 107.
Zhang G, Xu Y, Zhou H, fang. Esculetin inhibits proliferation, invasion, and migration of laryngeal cancer in vitro and in vivo by inhibiting Janus Kinas (JAK)-signal transducer and activator of transcription-3 (STAT3) activation. Medicine Science Monitor. 2019; 25 :7853-7863. DOI: 10.12659/MSM.916246 - 108.
Daly AK. Optimal dosing of warfarin and other coumarin anticoagulants: The role of genetic polymorphisms. Archives of Toxicology. 2013; 87 (3):407-420. DOI: 10.1007/s00204-013-1013-9 - 109.
Cravotto G, Nano GM, Palmisano G, Tagliapietra S. An asymmetric approach to coumarin anticoagulants via hetero-diels-alder cycloaddition. Tetrahedron: Asymmetry. 2001; 12 (5):707-709. DOI: 10.1016/S0957-4166(01)00124-0 - 110.
Shahab S, Sheikhi M, Khaleghian M, Kumar R, Murashko M. DFT study of physisorption effect of CO and CO2 on furanocoumarins for air purification. Journal of Environmental Chemical Engineering. 2018; 6 (4):4784-4796. DOI: 10.1016/j.jece.2018.07.019 - 111.
Dawe RS, Ibbotson SH. Drug-induced photosensitivity. Dermatologic Clinics. 2014; 32 (3):363-368. DOI: 10.1016/j.det.2014.03.014 - 112.
Gonzalez ME. The HIV-1 Vpr protein: A multifaceted target for therapeutic intervention. International Journal of Molecular Science. 2017; 18 (1):1-21. DOI: 10.3390/ijms18010126