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Synlett 2025; 36(01): 59-64
DOI: 10.1055/a-2312-0444
DOI: 10.1055/a-2312-0444
letter
Unexpected One-Pot Synthesis of 3-Cinnamoyl-3-hydroxyphthalide Derivatives
The authors would like to thank the National Research Council of Thailand (NRCT: NRCT5-RSA63002-10), the Graduate School, Kasetsart University (through the Graduate School Fellowship Program), the Kasetsart University Research and Development Institute (KURDI), the Center of Excellence for Innovation in Chemistry (PERCH-CIC), the Ministry of Higher Education, Science, Research and Innovation, the Thailand Toray Science Foundation (TTSF), and the Department of Chemistry and Faculty of Science, Kasetsart University, for financial support.
Abstract
A new and simple method to prepare 3-cinnamoyl-3-hydroxyphthalide derivatives from 2-hydroxy-3-methyl-1,4-naphthoquinone and substituted benzaldehydes was unexpectedly uncovered. The reaction was conveniently performed in DMSO at 100 °C with K3PO4 as a base and AlCl3 as a catalyst. We propose that the reaction proceeds by a cascade process involving nucleophilic addition followed by demethylation and rearrangement. The products were typically obtained in moderate to good yields. The highest yield (95%) was obtained when the reaction of 2-bromobenzaldehyde was performed for 24 hours. X-ray crystallography of the product derived from 2-fluorobenzaldehyde unequivocally confirmed the structure of the hydroxyphthalide derivatives.
Key words
hydroxyphthalides - one-pot synthesis - cascade reaction - natural product - benzaldehydesSupporting Information
- Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/a-2312-0444.
- Supporting Information
Publikationsverlauf
Eingereicht: 04. März 2024
Angenommen nach Revision: 23. April 2024
Accepted Manuscript online:
23. April 2024
Artikel online veröffentlicht:
03. Mai 2024
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References and Notes
- 1a Pettit GR, Numata A, Iwamoto C, Usami Y, Yamada T, Ohishi H, Cragg GM. J. Nat. Prod. 2006; 69: 323
- 1b Boonphong S, Puangsombat P, Baramee A, Mahidol C, Ruchirawat S, Kittakoop P. J. Nat. Prod. 2007; 70: 795
- 2 Kraus GA, Thite A, Liu F. Tetrahedron Lett. 2009; 50: 5303
- 3 Narita K, Nakamura K, Abe Y, Katoh T. Eur. J. Org. Chem. 2011; 4985
- 4 Thanetchaiyakup A, Borwornpinyo S, Rattanarat H, Kanjanasirirat P, Jearawuttanakul K, Seemakhan S, Chuanopparat N, Ngernmeesri P. Tetrahedron Lett. 2021; 82: 153365
- 5a Zhu R, Xing L, Wang X, Cheng C, Liu B, Hu Y. Synlett 2007; 2267
- 5b Hackl CM, Schoenhacker-Alte B, Klose MH. M, Henke H, Legina MS, Jakupec MA, Berger W, Keppler BK, Brüggemann O, Teasdale I, Heffeter P, Kandioller W. Dalton Trans. 2017; 46: 12114
- 6a Mizuno CS, Rimando AM, Duke SO. J. Agric. Food Chem. 2010; 58: 4353
- 6b Orita H, Shimizu M, Hayakawa T, Takehira K. Bull. Chem. Soc. Jpn. 1989; 62: 1652
- 7 Wei X, Zeng Y, Sun C, Meng F, Wang Y. Fitoterapia 2022; 160: 105223
- 8a Brady SF, Wagenaar MM, Singh MP, Janso JE, Clardy J. Org. Lett. 2000; 2: 4043
- 8b Singh MP, Janso JE, Brady SF. Mar. Drugs 2007; 5: 71
- 9 Liberra K, Jansen R, Lindequist U. Pharmazie 1998; 53: 578
- 10 Henkel T, Müller H, Schmidt D, Wollweber H. DE 19611366 1997
- 11 Correa WA, das Neves SC, Oliveira RJ, Kassuya CA, Navarro SD, Faustino Martins AC, Saroja B, Mitsuyasu B, Ostaciana M F da Silveira I, Vitor N, Coelho HR. S, Vilela ML. B, do Nascimento VA, de Lima DP, Beatriz A, da Silva Gomes R. Chem. Res. Toxicol. 2024; 37: 259
- 12a Gach J, Olejniczak T, Pannek J, Boratyński F. Molecules 2023; 28: 5423
- 12b Yang H, Hu G.-Y, Chen J, Wang Y, Wang Z.-H. Bioorg. Med. Chem. Lett. 2007; 17: 5210
- 13 Sun P, Liu J, Wang D, Chen Q, Wu W, Xiao H, Yang D, Fang R, Zhang Q, Zhou H, Xu J. CN 115960031 2023
- 14 3-Hydroxy-3-[(2E)-3-(2-iodophenyl)prop-2-enoyl]-2-benzofuran-1(3H)-one (11a):Typical Procedure Compound 9 (50 mg, 0.27 mmol), AlCl3 (7 mg, 0.05 mmol), 2-iodobenzaldehyde (6a) (0.43 mmol), and K3PO4 (169 mg, 0.80 mmol) were dissolved in DMSO (3 mL), and the mixture was stirred at 100 °C for 48 h. The resulting mixture was allowed to cool to r.t., diluted with H2O (50 mL), and extracted with EtOAc (3 × 50 mL). The organic extracts were combined, washed with sat. aq NH4Cl, dried (Na2SO4), and concentrated under reduced pressure. The residue was purified by flash column chromatography [silica gel EtOAc–hexanes (1:3 and 1:2)] to give a yellow-brown solid; yield: 46 mg (43%); mp 134–136 °C. IR (neat): 3376, 1776, 1743, 1689 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.13 (d, J = 15.5 Hz, 1 H), 8.02 (dt, J = 7.5, 1.0 Hz, 1 H), 7.87 (dd, J = 8.0, 1.2 Hz, 1 H), 7.77 (td, J = 7.5, 1.2 Hz, 1 H), 7.70 (td, J = 7.5, 1.1 Hz, 1 H), 7.52 (dt, J = 7.5, 1.0 Hz, 1 H), 7.35 (dd, J = 7.9, 1.7 Hz, 1 H), 7.29 (ddd, J = 7.3, 1.2, 0.6 Hz, 1 H), 7.06 (ddd, J = 8.0, 7.3, 1.7 Hz, 1 H), 6.30 (d, J = 15.5 Hz, 1 H), 5.88 (br s, 1 H). 13C{1H} NMR (100 MHz, CDCl3): δ = 189.7, 168.3, 152.0, 145.1, 140.5, 136.8, 135.6, 132.7, 131.9, 128.8, 128.0, 127.5, 126.3, 123.6, 119.2, 102.6, 102.4. HRMS (ESI): m/z [M + Na]+ calcd for C17H11INaO4: 428.9594; found: 428.9590.
- 15a Thanetchaiyakup A, Rattanarat H, Chuanopparat N, Ngernmeesri P. Tetrahedron Lett. 2018; 59: 1014
- 15b Thongaram P, Borwornpinyo S, Kanjanasirirat P, Jearawuttanakul K, Kongsema M, Chuanopparat N, Ngernmeesri P. Tetrahedron 2020; 76: 131473
- 15c Taweesak P, Thongaram P, Kraikruan P, Thanetchaiyakup A, Chuanopparat N, Hsieh H.-P, Uang B.-J, Ngernmeesri P. J. Org. Chem. 2021; 86: 1955
- 16 CCDC 2311144 contains the supplementary crystallographic data for compound 6c. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures. See also the Supporting Information for more details.