An Atom-Economical Approach to the Synthesis of Potentially Bioactive 2H-Chromenes via CuI-Catalyzed Reactions of Alkyl/Aryl-(E)-(o-Propar­gyloxy)styryl Ketones

Abstract

A series of potentially bioactive 2H-chromenes have been synthesized in good yields (60–82%) via CuI-catalyzed reactions of alkyl/aryl-(E)-(o-propargyloxy)styryl ketones in an atom-economical approach.

Keywords

aldol condensation - alkyl/aryl-(E)-(o-propargyl­oxy)styryl ketones - copper(I) iodide - 2H-chromenes - atom economy

• References and Notes

• 1a Hepworth JD. Pyrans and Fused Pyrans: Synthesis and Applications . In Comprehensive Heterocyclic Chemistry . Vol. 3. Katrizky AR, Rees CW. Pergamon; Oxford: 1984: 737
• 1b Milcent R, Chau F. Chimie Organique Hétérocyclique . EDP Sciences; Les Ulis: 2003: 434
• 2 Menut C, Bessiere JM, Ntalani H, Verin P, Henriques AT, Limberger R. Phytochemistry 2000; 53: 975
• 3 McKee TC, Fuller RW, Covington CD, Cardellina JH, Gulakowski RJ, Krepps BL, McMahon JB, Boyd MR. J. Nat. Prod. 1996; 59: 754
• 4 Nazarian Z, Emami S, Heydari S, Ardestani SK, Nakhjiri M, Poorrajab F, Shafiee A, Foroumadi A. Eur. J. Med. Chem. 2010; 45: 1424
• 5 Elomri A, Mitaku S, Michel S, Skaltsounis A.-L, Tillequin F, Koch M, Pierre A, Guilbaud N, Leonce S, Kraus-Berthier L, Rolland Y, Atassi G. J. Med. Chem. 1996; 39: 4762
• 6a Kidwai M, Saxena S, Khan MK. R, Thukral SS. Bioorg. Med. Chem. Lett. 2005; 15: 4295
• 6b Tahtaoui C, Demailly A, Guidemann C, Joyeux C, Schneider P. J. Org. Chem. 2010; 75: 3781
• 7 Lago JH. G, Ramos CS, Casanova DC. C, Morandim A de A, Bergamo DC. B, Cavalheiro AJ, Bolzani V da S, Furlan M, Guimarães EF, Young MC. M, Kato MJ. J. Nat. Prod. 2004; 67: 1783
• 8 Bernard CB, Krishnamurty HG, Chauret D, Durst T, Philogene BJ. R, Sanchez Vindas P, Hasbun C, Poveda L, San Roman L, Arnason JT. J. Chem. Ecol. 1995; 21: 801
• 9 Mukai K, Okabe K, Hosose H. J. Org. Chem. 1989; 54: 557
• 10a Paramonov S, Delbaere S, Fedorova O, Fedorov Y, Lokshin V, Samat A, Vermeersch GJ. Photochem. Photobiol. A 2010; 209: 111
• 10b Evans RA, Such GK. Aust. J. Chem. 2005; 58: 825
• 11 Hanamoto T, Shindo K, Matsuoka M, Kiguchi Y, Kondo M. J. Chem. Soc., Perkin Trans. 1 2000; 103
• 12 Varma RS, Dahiya R. J. Org. Chem. 1998; 63: 8038
• 13a Wang Q, Finn MG. Org. Lett. 2000; 2: 4063
• 13b Kabalka GW, Venkataiah B, Das BC. Synlett 2004; 2194
• 13c Petasis NA, Butkevich AN. J. Organomet. Chem. 2009; 694: 1747
• 14a Chang S, Grubbs RH. J. Org. Chem. 1998; 63: 864
• 14b Wipf P, Weiner WS. J. Org. Chem. 1999; 64: 5321
• 14c van Otterlo WA. L, Ngidi EL, Kuzvidza S, Morgans GL, Moleele SS, de Koning CB. Tetrahedron 2005; 61: 9996
• 15 Kaye PT, Nocanda XW. J. Chem. Soc., Perkin Trans. 1 2000; 1331
• 16 Hlubeck J, Ritchie E, Taylor WC. Tetrahedron Lett. 1969; 10: 1369
• 17 Iyer M, Trivedi GR. Synth. Commun. 1990; 20: 1347
• 18 Parker KA, Mindt TL. Org. Lett. 2001; 3: 3875
• 19 Ye LW, Sun X.-L, Zhu C.-Y, Tang Y. Org. Lett. 2006; 8: 3853
• 20 Worlikar SA, Kesharwani T, Yao T, Larock RC. J. Org. Chem. 2007; 72: 1347
• 21 Lykakis IN, Efe C, Gryparis C, Stratakis M. Eur. J. Org. Chem. 2011; 2334
• 22 Liu F, Evans T, Das BC. Tetrahedron Lett. 2008; 49: 1578
• 23 Bera K, Sarkar S, Biswas S, Maiti S, Jana U. J. Org. Chem. 2011; 76: 3539
• 24 Majumdar KC, Sinha B, Ansary I, Chakravorty S. Synlett 2010; 1407
• 25 Majumdar KC, Ansary I, Sinha B, Roy B, Sridhar B. Synthesis 2011; 3287
• 26 Typical Procedure for the Synthesis of (E)-4-(6-Methyl-2H-chromen-3-yl)but-3-en-2-one (9a): A mixture of compound 7a (150 mg, 0.70 mmol), and CuI (14 mg, 10 mol%) was stirred in dry DMF (4 mL) at 100 °C for 2 h. The reaction mixture was cooled to r.t., and then it was poured into H₂O (10 mL). The aqueous phase was extracted with CH₂Cl₂ (3 × 20 mL), the organic layer was washed with H₂O (3 × 15 mL), brine (20 mL), and then dried over anhyd Na₂SO₄. The solvent was removed under reduced pressure to give a crude mass which was chromatographed over silica gel (230–400 mesh) using EtOAc–PE (1:19 v/v) as an eluent to afford the 2H-chromene 9a as a sole product; yield 68%; mp 68 °C. IR (KBr): ν_max = 2918, 1682 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.26 (s, 3 H), 2.33 (s, 3 H), 4.93 (s, 2 H), 6.03 (d, 1 H, J = 16.4 Hz), 6.73–6.75 (m, 2 H), 6.89 (s, 1 H), 6.99 (dd, 1 H, J = 8.4, 1.6 Hz), 7.21 (d, 1 H, J = 16.4 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 20.5, 27.7, 65.0, 115.6, 121.6, 125.5, 128.3, 128.7, 131.1, 131.6, 132.0, 140.4, 152.4, 198.0. ESI-HRMS: m/z calcd for C₁₄H₁₄O₂Na [M + Na]: 237.0892; found: 237.0931
• 27 Yin K, Li C.-Ju, Li J, Jia X.-S. Appl. Organomet. Chem. 2011; 25: 16
• 28a Kumar K, Jolly RS. Tetrahedron Lett. 1998; 39: 3047
• 28b Paik S.-J, Son SU, Chung YK. Org. Lett. 1999; 1: 2045
• 28c Lee SI, Park SY, Park JH, Chung YK, Han JW. Bull. Korean Chem. Soc. 2007; 28: 1919
• 28d Kim SM, Park JH, Chung YK. Chem. Commun. 2011; 47: 6719
• 29 Piers E, Lu Y.-F. J. Org. Chem. 1989; 54: 2267