Sonogashira Reactions of 2,3,4,5-Tetrabromofuran: Synthesis of 2,3,4,5-Tetraalkynylfurans, 2,3,5-Trialkynylfurans and 2,5-Dialkynylfurans

Abstract

2,3,4,5-Tetrabromofuran is transformed into a variety of alkynyl-substituted furans by regioselective Sonogashira cross-coupling reactions. In this context, the first 2,3,4,5-tetraalkynylfurans and 2,3,5-trialkynylfurans were prepared. 2,3,4,5-Tetraalkynylfurans and 2,5-dialkynyl-3,4-diarylfurans show interesting fluorescence properties.

Key words

catalysis - palladium - Sonogashira reaction - furan - regio­selectivity - fluorescence

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• 26 General Procedure for Sonogashira Coupling ReactionsA suspension of tetrabromofuran (1), Pd(PPh₃)₂Cl₂ (10 mol%), CuI (5 mol%) in diisopropylamine was degassed three times in a pressure tube. The acetylene (1.2 equiv per bromine atom) was added using a syringe. The mixture was heated at the indicated temperature (60–80 °C) for 2–4 h. The reaction mixture was filtered and the residue was washed with CH₂Cl₂. The filtrate was washed with a saturated solution of ammonium chloride (2 x 25 mL), water (2 x 25 mL) and was subsequently dried over anhydrous Na₂SO₄. The solvent was removed in vacuo. The product was purified by column chromatography (silica gel, EtOAc–heptanes).3,4-Dibromo-2,5-bis[(4-tert-butylphenyl)ethynyl]furan (3a)Starting with 1 (150 mg; 0.40 mmol), 4-tert-butylphenyl-acetylene (2a) (0.16 mL, 0.94 mmol), CuI (5 mol%), Pd(PPh₃)₂Cl₂ (10 mol%), and diisopropylamine (5 mL), 3a was isolated as a white solid (163 mg, 78%); mp 197–199 °C. ¹H NMR (300 MHz, CDCl₃): δ = 1.36 (s, 18 H, CH₃), 7.40 (d, 4 H, J = 8.6 Hz), 7.51 (d, 4 H, J = 8.6 Hz). ¹³C NMR (75.4 MHz, CDCl₃): δ = 31.1 (CH₃), 34.9, 81.5, 98.8, 109.3, 118.8 (C), 125.5, 132.3 (CH), 136.7, 152.6 (C). IR (KBr): ν = 2952 (w), 1497 (m), 1461 (m), 1362 (m), 1266 (m), 1102 (m), 1013 (m), 923 (w), 833 (s) cm^–1. GC-MS (EI, 70 eV): m/z (%) = 536 (M⁺, [⁷⁹Br, ⁷⁹Br], 30), 538 (M⁺, [⁷⁹Br, ⁸¹Br], 100), 540 (M⁺, [⁸¹Br, ⁸¹Br], 62), 523 (52), 508 (2), 493 (4), 467 (3), 350 (3), 314 (18), 299 (26), 254 (15), 226 (9). HRMS (EI, 70 eV): calcd for C₂₈H₂₆Br₂O (M⁺, [⁷⁹Br, ⁷⁹Br]: 536.03449; found 536.03353; calcd for C₂₈H₂₆Br₂O (M⁺, [⁷⁹Br, ⁸¹Br]: 538.03245; found 538.03238; calcd for C₂₈H₂₆Br₂O (M⁺, [⁸¹Br, ⁸¹Br]: 540.03040; found 540.03176