Facile iron(III) chloride hexahydrate catalyzed synthesis of coumarins

Prateeptongkum, Saisuree; Duangdee, Nongnaphat; Thongyoo, Panumart

doi:10.3998/ark.5550190.p008.947

Cited by 12 publications

(8 citation statements)

References 35 publications

(35 reference statements)

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“…Coumarin 2j was prepared from 1j (61.0 mg, 0.26 mmol), 1-fluoro-2,4,6trimethylpyridinium trifluoromethanesulfonate (94.3 mg, 0.31 mmol), Cu(OAc) 2 (2.4 mg, 0.013 mmol), p-TsOH (49.9 mg, 0.26 mmol), and PdCl 2 (CH 3 CN) 2 (6.8 mg, 0.026 mmol) in mesitylene (1 mL). The mixture was stirred at 70 °C for 24 h, and after the work-up, flash column chromatography (silica gel, hexane/EtOAc 7/3) afforded 2j (29.8 mg, 49%) as a solid, whose data are coincidental with those reported: 71…”

Section: ■ Experimental Sectionsupporting

confidence: 67%

“…Coumarin 2j was prepared from 1j (61.0 mg, 0.26 mmol), 1-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate (94.3 mg, 0.31 mmol), Cu(OAc) 2 (2.4 mg, 0.013 mmol), p -TsOH (49.9 mg, 0.26 mmol), and PdCl 2 (CH 3 CN) 2 (6.8 mg, 0.026 mmol) in mesitylene (1 mL). The mixture was stirred at 70 °C for 24 h, and after the work-up, flash column chromatography (silica gel, hexane/EtOAc 7/3) afforded 2j (29.8 mg, 49%) as a solid, whose data are coincidental with those reported: mp (CH 2 Cl 2 ): 141–143 °C [lit . mp (EtOH:H 2 O) 146–148 °C]; IR (ATR) 1710 cm –1 (CO); 1 H NMR (CDCl 3 , 300 MHz): δ 1.21 (t, J = 7.3 Hz, 3H, CH 3 ), 2.94 (q, J = 7.3 Hz, 2H, CH 2 ), 3.84 (s, 3H, OCH 3 ), 3.87 (s, 3H, OCH 3 ), 6.00 (s, 1H, H 3 ), 6.30 (d, J = 2.4 Hz, 1H, H 6 ), 6.45 (d, J = 2.4 Hz, 1H, H 8 ); 13 C{ 1 H} NMR (CDCl 3 , 75.5 MHz): δ 13.5 (CH 3 ), 29.4 (CH 2 ), 55.7 (OCH 3 ), 55.8 (OCH 3 ), 93.6 (C 8 ), 95.6 (C 6 ), 104.3 (C 4a ), 109.7 (C 3 ), 157.2 (C 8a ), 158.8 (C 4 ), 159.9, 162.6 (C 5 , C 7 ), 161.4 (CO); MS (EI) m/z (rel intensity) 235 (M + + 1, 15), 234 (M + , 100), 207 (12), 206 (86), 205 (16), 191 (52), 161 (12), 103 (11); HRMS (CI) Calcd.…”

Section: Methodsmentioning

confidence: 99%

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Pd(II)-Catalyzed Fujiwara–Moritani Reactions for the Synthesis and Functionalization of Substituted Coumarins

et al. 2021

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Highly substituted coumarins, privileged and versatile scaffolds for bioactive natural products and fluorescence imaging, are obtained via a Pd(II)-catalyzed direct C–H alkenylation reaction (Fujiwara–Moritani reaction), which has emerged as a powerful tool for the construction and functionalization of heterocyclic compounds because of its chemical versatility and its environmental advantages. Thus, a selective 6-endo cyclization led to 4-substituted coumarins in moderate yields. Selected examples have been further functionalized in C3 through a second intermolecular C–H alkenylation reaction to give coumarin-acrylate hybrids, whose fluorescence spectra have been measured.

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Section: ■ Experimental Sectionsupporting

confidence: 67%

Section: Methodsmentioning

confidence: 99%

Pd(II)-Catalyzed Fujiwara–Moritani Reactions for the Synthesis and Functionalization of Substituted Coumarins

et al. 2021

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“…Nine synthetic coumarin analogs were submitted to the biotransformation experiments. All coumarins used as substrates were obtained according to known methods through a Pechmann reaction, and all of their spectroscopic data were identical to those previously described for 7-hydroxy-4-methyl-2 H -2-chromenone ( 1 ) [32], 5,7-dihydroxy-4-methyl-2 H -chromen-2-one ( 2 ) [33], 7,8-dihydroxy-4-methyl-2 H -chromen-2-one ( 3 ) [34], 7-hydroxy-2,3-dihydrocyclopenta[ c ]chromen-4(1 H )-one ( 4 ) [33], 7,9-dihydroxy-2,3-dihydrocyclopenta[ c ]chromen-4(1 H )-one ( 5 ) [33], 6,7-dihydroxy-2,3-dihydrocyclopenta[ c ]chromen-4(1 H )-one ( 6 ) [35], methyl 2-(7,8-dihydroxy-2-oxo-2 H -chromen-4-yl)acetate ( 7 ) [36], methyl 2-(5,7-dihydroxy-2-oxo-2 H -chromen-4-yl)acetate ( 8 ) [37], and methyl 2-(7-hydroxy-2-oxo-2 H -chromen-4-yl)acetate ( 9 ) [38].…”

Section: Methodsmentioning

confidence: 99%

Mapping the Biotransformation of Coumarins through Filamentous Fungi

et al. 2019

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Natural coumarins are present in remarkable amounts as secondary metabolites in edible and medicinal plants, where they display interesting bioactivities. Considering the wide enzymatic arsenal of filamentous fungi, studies on the biotransformation of coumarins using these microorganisms have great importance in green chemical derivatization. Several reports on the biotransformation of coumarins using fungi have highlighted the achievement of chemical analogs with high selectivity by using mild and ecofriendly conditions. Prompted by the enormous pharmacological, alimentary, and chemical interest in coumarin-like compounds, this study evaluated the biotransformation of nine coumarin scaffolds using Cunninghamella elegans ATCC 10028b and Aspergillus brasiliensis ATCC 16404. The chemical reactions which were catalyzed by the microorganisms were highly selective. Among the nine studied coumarins, only two of them were biotransformed. One of the coumarins, 7-hydroxy-2,3-dihydrocyclopenta[c]chromen-4(1H)-one, was biotransformed into the new 7,9-dihydroxy-2,3-dihydrocyclopenta[c]chromen-4(1H)-one, which was generated by selective hydroxylation in an unactivated carbon. Our results highlight some chemical features of coumarin cores that are important to biotransformation using filamentous fungi.

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“…Infrared spectra were performed with a Perkin Elmer FT-IR Spectrum GX. The preparations of compounds 1 -5 were achieved according to the previous work [27,28].…”

Section: Materials and Instrumentationmentioning

confidence: 99%

Evaluation of Cytotoxicity and Apoptosis Induced by Coumarin Hydrazide-Hydrazone Derivatives in Human Hepatocellular Carcinoma Cell Line

Prateeptongkum,

Duangdee,

Mahavorasirikul

2024

Trends Sci

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Coumarin and aryl hydrazide-hydrazone have attracted our attention due to their vast biological properties. Previous studies suggested that coumarin-tethered aryl hydrazide-hydrazone showed potent activities against HepG2. In the present study, we investigated the cytotoxic potency of the coumarin derivatives 1 - 3 to compare with coumarin hydrazine-hydrazone hybrids 4 and 5 against hepatocellular carcinoma HepG2 and LH86 cell lines. Among the tested coumarins, hybrids 4 and 5 showed highly potent activity against HepG2 with IC50 values of 17.82 ± 2.79 and 7.87 ± 0.88 𝜇g/mL, respectively. The hybrid 4 also showed the strongest activity against LH86 cell line with IC50 values of 48.32 ± 2.64 𝜇g/mL. Further, we have studied the mechanism of action of the hybrid compounds 4 and 5 in HepG2 cells via the flow-cytometry analysis and the activation of the caspase-3 and caspase-7. The results showed that hybrids 4 and 5 obviously inhibited the proliferation of HepG2 cell line through inducing apoptosis. HIGHLIGHTS Focusing on coumarin and aryl hydrazide-hydrazone possess significant biological properties. We reported the preparation of coumarin hydrazine-hydrazone hybrids and evaluated their effects against hepatocellular carcinoma cell lines HepG2 and LH86. The hybrid compounds exhibited high potency against HepG2 and LH86. Flow-cytometry and caspase-3/7 expression analysis revealed that the hybrid compounds induced apoptosis in HepG2 cells. GRAPHICAL ABSTRACT

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Facile iron(III) chloride hexahydrate catalyzed synthesis of coumarins

Cited by 12 publications

References 35 publications

Pd(II)-Catalyzed Fujiwara–Moritani Reactions for the Synthesis and Functionalization of Substituted Coumarins

Pd(II)-Catalyzed Fujiwara–Moritani Reactions for the Synthesis and Functionalization of Substituted Coumarins

Mapping the Biotransformation of Coumarins through Filamentous Fungi

Evaluation of Cytotoxicity and Apoptosis Induced by Coumarin Hydrazide-Hydrazone Derivatives in Human Hepatocellular Carcinoma Cell Line

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