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; Zeeshan Ahmad; Sebastian Reimann; Muhammed Nawaz; Tamás Patonay; Peter Langer

doi:10.1055/s-0031-1291007

Synlett, Table of Contents

Synlett 2012; 23(10): 1463-1466
DOI: 10.1055/s-0031-1291007

letter

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

^aInstitut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany

^bDepartment of Chemistry, COMSATS Institute of Information Technology, Abbottabad, Pakistan

,

Zeeshan Ahmad

^aInstitut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany

,

Sebastian Reimann

^aInstitut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany

^cLeibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany

,

Muhammed Nawaz

^aInstitut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany

,

Tamás Patonay

^dDepartment of Organic Chemistry, University of Debrecen, 4032 Debrecen, Egyetem tér 1, Hungary

,

Peter Langer*

^aInstitut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany

^cLeibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany

› Author Affiliations

Abstract

All articles of this category

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

Full Text

References

References

1a Hou XL, Yang Z, Wong HN. C In Progress in Heterocyclic Chemistry . Vol. 15. Gribble GW, Gilchrist TL. Pergamon; Oxford: 2003: 167
1b Friedrichsen W In Comprehensive Heterocyclic Chemistry. Vol. 2. Katritzky AR, Rees CW, Scriven EF. V. Elsevier; Amsterdam: 1996: 359
1c Shea KM. Palladium in Heterocyclic Chemistry. Vol. 26. Elsevier; Amsterdam: 2007: 303

2a Culver P, Jacobs RS. Toxicon 1981; 19: 825
2b Missakian MG, Burreson BJ, Schever PJ. Tetrahedron 1975; 31: 2513
2c Shen YC, Chatervedula VS. P, Kuo YH. J. Nat. Prod. 2001; 64: 324
2d Karasawa D, Shatar S, Erdenechimeg A, Okamoto Y, Tateba H, Shimizu S. J. Essent. Oil. Res. 1995; 7: 255
2e Look SA, Burch NT, Fenical W. J. Org. Chem. 1985; 50: 5741
2f Kobayashi M, Mahmud T, Tajima H, Wang W.-Q, Aoki S, Nakagawa S, Mayumi T, Kitagawa I. Chem. Pharm. Bull. 1996; 44: 720
2g Chang HM, Cheng KP, Choang TF, Chow HF, Chui KY, Hon PM, Tan FW. L, Yang Y, Zhong ZP, Lee CM, Sham HL, Chan CF, Cui YX, Wong HN. C. J. Org. Chem. 1990; 55: 3537
2h Bernard R, Cardani C, Selva D, Baggini A, Pavan M. Tetrahedron Lett. 1967; 3893
2i Barma DK, Kundu A, Baati R, Mioskowski C, Falck JR. Org. Lett. 2002; 4: 1387

3a Brunton L, Lazo J, Keith P. The Pharmacological Basis of Therapeutics . McGraw-Hill; New York: 2005
3b Cadwallader DE. J. Am. Pharm. Assoc. 1975; NS15: 409

4a Tangallapally RP, Lee RE. B, Lenaerts AJ. M, Lee RE. Bioorg. Med. Chem. Lett. 2006; 16: 2584
4b Srivastava V, Negi AS, Kumar JK, Faridu U, Sisodia BS, Darokar MP, Luqman S, Khanuja SP. S. Bioorg. Med. Chem. Lett. 2006; 16: 911
4c Nagaraja GK, Kumaraswamy MN, Vaidya VP, Mahadeven KM. ARKIVOC 2006; (x): 1
4d Sondhi SM, Jain S, Rani R, Kumar A. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2007; 46: 1848

5 Lind P, Carlsson M, Eliasson B, Glimsdal E, Lindgren M, Lopes C, Boman L, Norman P. Mol. Phys. 2009; 107: 629
6 Greco NJ, Tor Y. Tetrahedron 2007; 63: 3515
7 Yamaguchi T, Irie M. J. Mater. Chem. 2006; 16: 4690
8 Lechel T, Dash J, Brudgam I, Reissig HU. Eur. J. Org. Chem. 2008; 3647

9a Dulop AP, Peters FN. The Furans . Reinhold Publishing; Baltimore: 1953: 35
9b Grieco P, Pogonowski C, Burke S. J. Org. Chem. 1975; 40: 542
9c Scott LT, Naples JO. Synthesis 1973; 209

10 Bisagni E, Marquet JP, Bourzat JD, Depin JJ, Andre-Louisfert J. Bull. Chem. Soc. Fr. 1971; 4041
11 Courmier RA, Grosshans CA, Skibbe SL. Synth. Commun. 1988; 7: 677
12 Sammond DM, Sammakia T. Tetrahedron Lett. 1996; 37: 6065

13a Zeni G, Larock RC. Chem. Rev. 2004; 104: 2285
13b Kirsch G, Hesse S, Comel A. Curr. Org. Synth. 2004; 1: 47
13c Marson C, Harper S, Wrigglesworth R. J. Chem. Soc., Chem. Commun. 1994; 1879

14 Mross G, Holtz E, Langer P. J. Org. Chem. 2006; 71: 8045
15 Marshall JA, Bennett C. J. Org. Chem. 1994; 59: 6110
16 Tso HH, Tsay H. Tetrahedron. Lett. 1997; 38: 6869
17 Mortensn DS, Rodriguez AL, Carlson KE, Sun J, Katzenellenbogen BS, Katzenellenbogen JA. J. Med. Chem. 2001; 44: 3838

For reviews of site-selective palladium(0)-catalyzed cross-coupling reactions, see:

18a Schröter S, Stock C, Bach T. Tetrahedron 2005; 61: 2245
18b Schnürch M, Flasik R, Khan AF, Spina M, Mihovilovic MD, Stanetty P. Eur. J. Org. Chem. 2006; 3283
18c Wang R, Manabe K. Synthesis 2009; 1405
18d For a simple guide for the prediction of the site selectivity of palladium-catalyzed cross-coupling reactions based on ¹H NMR data of the nonhalogenated derivatives, see: Handy ST, Zhang Y. Chem. Commun. 2006; 299

19a Bach T, Krüger L. Eur. J. Org. Chem. 1999; 2045
19b Stock C, Höfer F, Bach T. Synlett 2005; 511
19c Carpita A, Rossi R. Tetrahedron 1985; 41: 1919
19d Wellmar U, Hörnfeldt A.-B, Gronowitz S. J. Heterocycl. Chem. 1995; 32: 1159
19e Bach T, Krüger L. Synlett 1998; 1185
19f Bach T, Krüger L. Eur. J. Org. Chem. 1999; 2045

20a Sulikowski GA, Agnelli F, Corbett RM. J. Org. Chem. 2000; 65: 337
20b Bellina F, Falchi E, Rossi R. Tetrahedron 2003; 59: 9091

21 Hussain M, Khera RA, Nguyen TH, Langer P. Org. Biomol. Chem. 2011; 9: 370
22 Dang TT, Dang TT, Rasool N, Villinger A, Langer P. Adv. Synth. Catal. 2009; 351: 1595

23a Neenan TX, Whitesides GM. J. Org. Chem. 1988; 53: 2489
23b For 2,5-di(alkynyl)thiophenes, see: Eichhorn SH, Paraskos AJ, Kishikawa K, Swager TM. J. Am. Chem. Soc. 2002; 124: 12742

24 Ullah F, Dang TT, Heinicke J, Villinger A, Langer P. Synlett 2009; 838
25 Shoppee CW. J. Chem. Soc., Perkin Trans. 1 1985; 45
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

Supplementary Material

Supporting Information