Synlett 2012; 23(10): 1463-1466
DOI: 10.1055/s-0031-1291007
letter
© Georg Thieme Verlag Stuttgart · New York

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

Imran Malik
a  Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
b  Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad, Pakistan
,
Zeeshan Ahmad
a  Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
,
Sebastian Reimann
a  Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
c  Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany
,
Muhammed Nawaz
a  Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
,
Tamás Patonay
d  Department of Organic Chemistry, University of Debrecen, 4032 Debrecen, Egyetem tér 1, Hungary
,
Peter Langer*
a  Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
c  Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany
› Author Affiliations
Further Information

Publication History

Received: 21 March 2012

Accepted: 23 March 2012

Publication Date:
18 May 2012 (online)


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.

Supporting Information

 
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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