Iodine-Catalyzed Simple and Efficient Synthesis of 1,3,5-Triarylbenzenes and 2,3-Dihydrobenzofuran Derivatives under Mild Reaction Conditions

Abstract

The I₂-catalyzed cyclization reaction of chalcones and 2-aryl propionaldehydes or isobutyraldehyde has been developed for the synthesis of 1,3,5-triarylbenzenes and 2,3-dihydrobenzofuran derivatives. This reaction tolerates a wide range of functional groups. Moreover, this method features an inexpensive catalyst and available starting materials.

Key words

1,3,5-triarylbenzenes - 2,3-dihydrobenzofuran scaffolds - chalcone - annulation - I₂

Publication History

Received: 23 April 2023

Accepted after revision: 10 May 2023

Article published online:
12 June 2023

• References and Notes

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• 11 General Procedure for the Synthesis of 1,3,5-Triarylbenzenes Chalcones 1 (0.5 mmol), 2-phenylpropanal 2 (5.0 mL), and I₂ (38.1 mg, 0.25 mmol) were loaded into a 10 mL sealed tube. The reaction mixture was stirred at 110 ℃. After completion, the reaction was quenched by the addition of saturated aqueous Na₂S₂O₃ (15 mL) and extracted with dichloromethane (3 × 10 mL). The combined organic extracts were washed with H₂O (20 mL) and brine (20 mL), dried with anhydrous Na₂SO₄, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (200–300 mesh) using PE/dichloromethane to give the product. 5′-Phenyl-1,1′:3′,1′′-terphenyl (3a) White solid; ¹H NMR (500 MHz, CDCl₃): δ = 7.79 (s, 3 H), 7.74–7.67 (m, 6 H), 7.48 (t, J = 7.6 Hz, 6 H), 7.44–7.32 (m, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 142.4, 141.2, 128.9, 127.6, 127.4, 125.2.
• 12 Chalcones 1 (0.5 mmol), isobutyraldehyde 2 (5.0 mL), and I₂ (63.3 mg, 0.25 mmol) were loaded into a 20 mL sealed tube. The reaction mixture was stirred at 100 ℃ for 12 h. After completion, the reaction was quenched by the addition of saturated aqueous Na₂S₂O₃ (15 mL) and extracted with EtOAc (3 × 10 mL). The combined organic extracts were washed with H₂O (20 mL) and brine (20 mL), dried with anhydrous Na₂SO₄, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (200–300 mesh) using PE/Et₂O to give the product. 2-Isopropyl-3,3-dimethyl-4,6-diphenyl-2,3-dihydrobenzofuran (4a) White solid; mp 157–163 ℃. ¹H NMR (400 MHz, CDCl₃): δ = 7.44–7.36 (m, 10 H), 6.66 (s, 1 H), 3.92 (d, J = 6.4 Hz, 1 H), 2.28 (s, 3 H), 2.21‒2.15 (m, 1 H), 1.25 (s, 3 H),1.22 (d, J = 4.4 Hz, 3 H), 1.17 (s, 3 H), 1.09 (d, J = 4.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 157.0, 141.4, 141.1, 140.8, 136.7, 132.9, 129.7, 129.5, 128.0, 127.5, 127.0, 126.7, 124.5, 116.5, 97.4, 45.5, 29.2, 27.4, 22.7, 20.7, 20.0, 12.9. IR (thin film): 3054, 3032, 2976, 2896, 1568, 1474, 1392, 985, 763. HRMS (ESI): m/z calcd for C₂₆H₂₉O [M + H]⁺: 357.2213; found: 357.2207.
• 13 CCDC 22232941 (4b) and CCDC 2232940 (4i) contain the supplementary crystallographic data for this paper. These data can be obtained free charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.