Synthesis of Geranyloxycoumarin Derivatives under Mild Conditions Using Cs2CO3

Year 2022, Volume: 9 Issue: 1, 57 - 66, 28.02.2022

Sumi Hwang , Eonjoo Roh

https://doi.org/10.18596/jotcsa.996363

Cited By: 1

Abstract

In this study, the synthesis of various geranyloxycoumarin derivatives from hydroxycoumarin was obtained in good yield under mild conditions using Cs2CO3. In the synthesis of geranyloxycoumarin derivatives, when 4-hydroxycoumarin reacts with geranyl bromide under mild conditions due to tautomeric keto-enol forms, 4-geranyoxycoumarin (3a), C-alkylated coumarin (3aa) and structure 3ab formed by hydrolysis and decarboxylation from 3aa were formed products. In addition, the alkylation reaction of 3-OH, 5-OH, 6-OH, 7-OH, and 8-OH coumarin except 4-OH group produced a high yield.

Keywords

geranyloxycoumarin derivatives, 4-hydroxycoumarin, tautomeric keto-enol forms, coumarin compounds, geranyl bromide

References

• 1. Borges F, Roleira F, Milhazes N, Santana L, Uriarte E. Simple Coumarins and Analogues in Medicinal Chemistry: Occurrence, Synthesis and Biological Activity. CMC. 2005 Apr 1;12(8):887–916.
• 2. Niu X, Xing W, Li W, Fan T, Hu H, Li Y. Isofraxidin exhibited anti-inflammatory effects in vivo and inhibited TNF-α production in LPS-induced mouse peritoneal macrophages in vitro via the MAPK pathway. International Immunopharmacology. 2012 Oct;14(2):164–71.
• 3. Berrino E, Milazzo L, Micheli L, Vullo D, Angeli A, Bozdag M, et al. Synthesis and Evaluation of Carbonic Anhydrase Inhibitors with Carbon Monoxide Releasing Properties for the Management of Rheumatoid Arthritis. J Med Chem. 2019 Aug 8;62(15):7233–49.
• 4. Zhao Y-L, Yang X-W, Wu B-F, Shang J-H, Liu Y-P, Zhi-Dai, et al. Anti-inflammatory Effect of Pomelo Peel and Its Bioactive Coumarins. J Agric Food Chem. 2019 Aug 14;67(32):8810–8.
• 5. Peperidou A, Bua S, Bozdag M, Hadjipavlou-Litina D, Supuran C. Novel 6- and 7-Substituted Coumarins with Inhibitory Action against Lipoxygenase and Tumor-Associated Carbonic Anhydrase IX. Molecules. 2018 Jan 12;23(1):153.
• 6. Chen LZ, Sun WW, Bo L, Wang JQ, Xiu C, Tang WJ, et al. New arylpyrazoline-coumarins: Synthesis and anti-inflammatory activity. European Journal of Medicinal Chemistry. 2017 Sep;138:170–81.
• 7. Zhu M, Ma L, Wen J, Dong B, Wang Y, Wang Z, et al. Rational design and Structure−Activity relationship of coumarin derivatives effective on HIV-1 protease and partially on HIV-1 reverse transcriptase. European Journal of Medicinal Chemistry. 2020 Jan;186:111900.
• 8. Liu Y-P, Yan G, Xie Y-T, Lin T-C, Zhang W, Li J, et al. Bioactive prenylated coumarins as potential anti-inflammatory and anti-HIV agents from Clausena lenis. Bioorganic Chemistry. 2020 Apr;97:103699.
• 9. Patil AD, Freyer AJ, Eggleston DS, Haltiwanger RC, Bean MF, Taylor PB, et al. The inophyllums, novel inhibitors of HIV-1 reverse transcriptase isolated from the Malaysian tree, Calophyllum inophyllum Linn. J Med Chem. 1993 Dec;36(26):4131–8.
• 10. Zhao J-W, Wu Z-H, Guo J-W, Huang M-J, You Y-Z, Liu H-M, et al. Synthesis and anti-gastric cancer activity evaluation of novel triazole nucleobase analogues containing steroidal/coumarin/quinoline moieties. European Journal of Medicinal Chemistry. 2019 Nov;181:111520.
• 11. Lin M-H, Wang J-S, Hsieh Y-C, Zheng J-H, Cho E-C. NO2 functionalized coumarin derivatives suppress cancer progression and facilitate apoptotic cell death in KRAS mutant colon cancer. Chemico-Biological Interactions. 2019 Aug;309:108708.
• 12. Eker Y, Şenkuytu E, Ölçer Z, Yıldırım T, Çiftçi GY. Novel coumarin cyclotriphosphazene derivatives: Synthesis, characterization, DNA binding analysis with automated biosensor and cytotoxicity. Journal of Molecular Structure. 2020 Jun;1209:127971.
• 13. Sanduja M, Gupta J, Singh H, Pagare PP, Rana A. Uracil-coumarin based hybrid molecules as potent anti-cancer and anti-bacterial agents. Journal of Saudi Chemical Society. 2020 Feb;24(2):251–66.
• 14. Ahmed EY, Abdel Latif NA, El-Mansy MF, Elserwy WS, Abdelhafez OM. VEGFR-2 inhibiting effect and molecular modeling of newly synthesized coumarin derivatives as anti-breast cancer agents. Bioorganic & Medicinal Chemistry. 2020 Mar;28(5):115328.
• 15. Maly DJ, Leonetti F, Backes BJ, Dauber DS, Harris JL, Craik CS, et al. Expedient Solid-Phase Synthesis of Fluorogenic Protease Substrates Using the 7-Amino-4-carbamoylmethylcoumarin (ACC) Fluorophore. J Org Chem. 2002 Feb 1;67(3):910–5.
• 16. 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 Collections. 2018 Aug;15–16:41–53.
• 17. Ostrowska K. Coumarin-piperazine derivatives as biologically active compounds. Saudi Pharmaceutical Journal. 2020 Feb;28(2):220–32.
• 18. Smyth T, Ramachandran VN, Smyth WF. A study of the antimicrobial activity of selected naturally occurring and synthetic coumarins. International Journal of Antimicrobial Agents. 2009 May;33(5):421–6.
• 19. Wang H, Xu W. Mito-methyl coumarin, a novel mitochondria-targeted drug with great antitumor potential was synthesized. Biochemical and Biophysical Research Communications. 2017 Jul;489(1):1–7.
• 20. Weber US, Steffen B, Siegers CP. Antitumor-activities of coumarin, 7-hydroxy-coumarin and its glucuronide in several human tumor cell lines. Res Commun Mol Pathol Pharmacol. 1998 Feb;99(2):193–206.
• 21. Liu H, Li Z, Yu L, Zhang Y. Antitumor activity and mechanisms of scoparone. J Zhong Guo Yao Li Tong Xun. 2005;22:40–1.
• 22. Liu W, Hua J, Zhou J, Zhang H, Zhu H, Cheng Y, et al. Synthesis and in vitro antitumor activity of novel scopoletin derivatives. Bioorganic & Medicinal Chemistry Letters. 2012 Aug;22(15):5008–12.
• 23. Zaragozá C, Monserrat J, Mantecón C, Villaescusa L, Zaragozá F, Álvarez‐Mon M. Antiplatelet activity of flavonoid and coumarin drugs. Vascular Pharmacology. 2016 Dec;87:139–49.
• 24. Revankar HM, Bukhari SNA, Kumar GB, Qin H-L. Coumarins scaffolds as COX inhibitors. Bioorganic Chemistry. 2017 Apr;71:146–59.
• 25. Huang H-Y, Ko H-H, Jin Y-J, Yang S-Z, Shih Y-A, Chen I-S. Dihydrochalcone glucosides and antioxidant activity from the roots of Anneslea fragrans var. lanceolata. Phytochemistry. 2012 Jun;78:120–5.
• 26. Khan S, Riaz N, Afza N, Malik A, Aziz-ur-Rehman, Iqbal L, et al. Antioxidant constituents from Cotoneaster racemiflora. Journal of Asian Natural Products Research. 2009 Jan 1;11(1):44–8.
• 27. Mangasuli SN, Hosamani KM, Managutti PB. Microwave assisted synthesis of coumarin-purine derivatives: An approach to in vitro anti-oxidant, DNA cleavage, crystal structure, DFT studies and Hirshfeld surface analysis. Heliyon. 2019 Jan;5(1):e01131.
• 28. Ambreen, Haque S, Singh V, Katiyar D, Ali Khan MT, Tripathi V, et al. Biotransformation of newly synthesized coumarin derivatives by Candida albicans as potential antibacterial, antioxidant and cytotoxic agents. Process Biochemistry. 2019 Dec;87:138–44.
• 29. Kavetsou E, Gkionis L, Galani G, Gkolfinopoulou C, Argyri L, Pontiki E, et al. Synthesis of prenyloxy coumarin analogues and evaluation of their antioxidant, lipoxygenase (LOX) inhibitory and cytotoxic activity. Med Chem Res. 2017 Apr;26(4):856–66.
• 30. Roussaki M, Zelianaios K, Kavetsou E, Hamilakis S, Hadjipavlou-Litina D, Kontogiorgis C, et al. Structural modifications of coumarin derivatives: Determination of antioxidant and lipoxygenase (LOX) inhibitory activity. Bioorganic & Medicinal Chemistry. 2014 Dec;22(23):6586–94.
• 31. Al-Majedy Y, Al-Duhaidahawi D, Al-Azawi K, Al-Amiery A, Kadhum A, Mohamad A. Coumarins as Potential Antioxidant Agents Complemented with Suggested Mechanisms and Approved by Molecular Modeling Studies. Molecules. 2016 Jan 23;21(2):135.
• 32. Yun B-S, Lee I-K, Ryoo I-J, Yoo I-D. Coumarins with Monoamine Oxidase Inhibitory Activity and Antioxidative Coumarino-lignans from Hibiscus s yriacus. J Nat Prod. 2001 Sep 1;64(9):1238–40.
• 33. Tamene D, Endale M. Antibacterial Activity of Coumarins and Carbazole Alkaloid from Roots of Clausena anisata. Advances in Pharmacological Sciences. 2019 Feb 3;2019:1–8.
• 34. Yang L, Wu L, Yao X, Zhao S, Wang J, Li S, et al. Hydroxycoumarins: New, effective plant-derived compounds reduce Ralstonia pseudosolanacearum populations and control tobacco bacterial wilt. Microbiological Research. 2018 Oct;215:15–21.
• 35. Ramírez-Pelayo C, Martínez-Quiñones J, Gil J, Durango D. Coumarins from the peel of citrus grown in Colombia: composition, elicitation and antifungal activity. Heliyon. 2019 Jun;5(6):e01937.
• 36. Shah V, Bose J, Shah R. Communication- New Synthesis of 4-Hydroxycoumarins. J Org Chem. 1960 Apr;25(4):677–8.
• 37. Cravotto G, Nano GM, Palmisano G, Tagliapietra S. 4-Hydroxycoumarin and related systems: Sitoselectivity of the mitsunobu reaction with prenyl alcohols. HETEROCYCLES. 2003;60:1351–8.
• 38. Patra P. 4-Chloro-3-formylcoumarin as a multifaceted building block for the development of various bio-active substituted and fused coumarin heterocycles: a brief review. New J Chem. 2021;45(32):14269–327.
• 39. Russell A, Frye JR. 2,6-dihydroxyacetophenone. Org Synth. 1941;21:22.
• 40. Shue Y-J, Yang S-C. Activator-free and one-pot C-allylation by simple palladium catalyst in water. Tetrahedron Letters. 2012 Mar;53(11):1380–4.
• 41. Woods LL, Sapp J. A New One-Step Synthesis of Substituted Coumarins. J Org Chem. 1962 Oct;27(10):3703–5.
• 42. Venturella P, Bellino A, Marino M, Maria L. Synthesis of terpenoid coumarins, an approach to the synthesis of Piloselliodan. Gazz Chim Italiana. 1982;112(9/10):433–4.
• 43. Iranshahi M, Jabbari A, Orafaie A, Mehri R, Zeraatkar S, Ahmadi T, et al. Synthesis and SAR studies of mono O-prenylated coumarins as potent 15-lipoxygenase inhibitors. European Journal of Medicinal Chemistry. 2012 Nov;57:134–42.
• 44. Khomenko TM, Zarubaev VV, Orshanskaya IR, Kadyrova RA, Sannikova VA, Korchagina DV, et al. Anti-influenza activity of monoterpene-containing substituted coumarins. Bioorganic & Medicinal Chemistry Letters. 2017 Jul;27(13):2920–5.
• 45. Orhan IE, Senol Deniz FS, Salmas RE, Durdagi S, Epifano F, Genovese S, et al. Combined molecular modeling and cholinesterase inhibition studies on some natural and semisynthetic O-alkylcoumarin derivatives. Bioorganic Chemistry. 2019 Mar;84:355–62.