Arylation of Aldehydes with Indoles Using 1,3-Diisopropylimidazolinium Tetrafluoroborate as a Recyclable Catalyst for the Synthesis of Bis(indolyl)methanes in Water

Abstract

Bis(indolyl)methanes have attracted considerable attention for their interesting biological activities. Green organic-catalytic synthesis has promoted the development of green chemistry, especially in aqueous-phase reaction systems. We have developed a green and efficient catalytic arylation of aldehydes with indoles using low-cost 1,3-diisopropylimidazolinium tetrafluoroborate as a recyclable and reusable catalyst for the synthesis of bis(indolyl)methanes in water.

Key words

organocatalysis - bisindolylmethanes - green chemistry - aqueous-phase reaction

Publication History

Received: 18 November 2024

Accepted after revision: 23 December 2024

Accepted Manuscript online:
23 December 2024

Article published online:
28 January 2025

• References and Notes

• 1 Zeng W, Han C, Mohammed S, Li S, Song Y, Sun F, Du Y. RSC Med. Chem. 2024; 15: 788
• 2 Hu W, Yan G, Ding Q, Cai J, Zhang Z, Zhao Z, Lei H, Zhu YZ. Biomed. Pharmacother. 2022; 150: 112957
• 3 Fan S, Meng Q, Xu J, Jiao Y, Zhao L, Zhang X, Sarkar FH, Brown ML, Dritschilo A, Rosen EM. Proc. Natl. Acad. Sci. U.S.A. 2013; 110: 18650
• 4 Kang J, Gao Y, Zhang M, Ding X, Wang Z, Ma D, Wang Q. J. Agric. Food Chem. 2020; 68: 7839
• 5 Liu X, Ma S, Toy PH. Org. Lett. 2019; 21: 9212
• 6a Shiri M, Zolfigol MA, Kruger HG, Tanbakouchian Z. Chem. Rev. 2010; 110: 2250
• 6b Teli P, Soni S, Teli S, Agarwal S. Top. Curr. Chem. 2024; 382: 8
• 6c Kolagkis PX, Galathri EM, Kokotos CG. Beilstein J. Org. Chem. 2024; 20: 379
• 6d Mandal K, Rana G, Nur A, Ghosh S, Jana U. Synlett 2024; 35: 2525
• 6e Chen X, Liu Y, Jin H, Zhou B. Synthesis 2022; 54: 1347
• 7 Joshi RS, Mandhane PG, Diwakar SD, Gill CH. Ultrason. Sonochem. 2010; 17: 298
• 8 Xia M, Wang S.-h, Yuan W.-b. Synth. Commun. 2004; 34: 3175
• 9 Galathri EM, Di Terlizzi L, Fagnoni M, Protti S, Kokotos CG. Org. Biomol. Chem. 2023; 21: 365
• 10 Liu C, Xiao Z, Wu S, Shen Y, Yuan K, Ding Y. ChemSusChem 2020; 13: 1997
• 11 Kamboj P, Tyagi V. Tetrahedron 2023; 148: 133679
• 12 Khanna L, Mansi Mansi, Yadav S, Misra N, Khanna P. Synth. Commun. 2021; 51: 2892
• 13 Galathri EM, Kuczmera TJ, Nachtsheim BJ, Kokotos CG. Green Chem. 2024; 26: 825
• 14 Alder RW, Blake ME, Bufali S, Butts CP, Orpen AG, Schütz J, Williams SJ. J. Chem. Soc., Perkin Trans. 1 2001; 1586
• 15a Li L, Yang D, Zhao Z, Song Y, Zhao L, Liu R, Liu G. Front. Chem. 2018; 6: 272
• 15b Chauhan J, Kwasny SM, Fletcher S, Opperman TJ, de Leeuw EP. H. Bioorg. Med. Chem. Lett. 2019; 29: 1849
• 15c Nielsen MM, Pedersen CM. Chem. Sci. 2022; 13: 6181
• 16 IiPrim·HBF₄ NH₄BF₄ (624 mg, 6 mmol) was added to a stirred solution of N,N′-diisopropylethylenediamine (719 mg, 5 mmol) and triethyl orthoformate (740 mg, 5 mmol) in EtOH (20 mL), and the mixture was refluxed overnight. When the reaction was complete (TLC), the mixture was concentrated in vacuo. H₂O (100 mL) was added to the residue and the mixture was extracted with CH₂Cl₂ (50 mL). The organic layer was dried and concentrated in vacuo to give a colorless solid. Purity (HPLC): >97%. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.41 (s, 1 H), 3.82–3.88 (m, 6 H), 1.25 (d, J = 8.0 Hz, 12 H). BIMs; General Procedure IiPrim·HBF₄ (0.1 mmol) was added to a stirred solution of the appropriate indole or N-methylindole (0.5 mmol) and aldehyde (0.3 mmol) in H₂O (2 mL), and the mixture was stirred at 80 °C for 1–3 h. When the reaction was complete (TLC), the mixture was diluted with EtOAc (5 mL) and the organic layer was dried and concentrated in vacuo. The residue was purified by column chromatography. 3,3′-(Phenylmethylene)bis-1H-indole (1a) White solid; yield: 91%. ¹H NMR (400 MHz, CDCl₃): δ = 7.79 (s, 2 H), 7.44 (d, J = 7.4 Hz, 2 H), 7.40 (d, J = 7.4 Hz, 2 H), 7.30–7.36 (m, 4 H), 7.24–7.27 (m, 3 H), 7.07 (t, J = 7.8 Hz, 2 H), 6.63 (s, 2 H), 5.92 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 144.13, 136.69, 128.73, 128.25, 127.06, 126.02, 123.10, 121.33, 119.87, 119.73, 119.22, 110.87, 40.19.