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Synlett 2010(18): 2775-2777  
DOI: 10.1055/s-0030-1258994
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Efficient Multicomponent Synthesis of Highly Functionalized Cyclopentenes

Mehdi Adib*a, Ehsan Sheikhia, Pouyan Haghshenasa, Hamid Reza Bijanzadehb
a School of Chemistry, University College of Science, University of Tehran, PO Box 14155-6455, Tehran, Iran
Fax: +98(21)66495291; e-Mail: madib@khayam.ut.ac.ir;
b Department of Chemistry, Tarbiat Modarres University, PO Box 14115-175, Tehran, Iran
Further Information

Publication History

Received 14 June 2010
Publication Date:
08 October 2010 (online)

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Abstract

An efficient, one-pot and multicomponent synthesis of dialkyl 5,5-dicyano-3-aryl-2-cyclopentene-1,2-dicarboxylates is described. A mixture of a phenacyl bromide, malononitrile, and a dialkyl acetylenedicarboxylate in the presence of triphenylphosphine and triethylamine undergo a smooth addition reaction in absolute ethanol at ambient temperature to afford the highly functionalized cyclopentenes in good to excellent yields.

Key words

phenacyl bromides - alkynes - cyclopentenes - multicomponent reactions - cyclizations - intramolecular Wittig reactions

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17

General Procedure for the Preparation of Compounds 4a-k A solution of the appropriate phenacyl bromide (1 mmol), malononitrile (1 mmol), and Et3N (1 mmol) in EtOH (3 mL) was stirred at ambient temperature for 1 h. After addition of Ph3P (1 mmol), a solution of the appropriate dialkyl acetylenedicarboxylate (1 mmol) in EtOH (2 mL) was dropwise added to the reaction mixture over 25 min, which then was stirred at ambient temperature for 5 h. The solvent was removed under reduced pressure, and the residue was purified by column chromatography (Merck silica gel 230-240 mesh) using n-hexane-EtOAc (3:1) as eluent. The solvent was removed and the product was obtained.
Dimethyl 5,5-Dicyano-3-phenyl-2-cyclopentene-1,2-dicarboxylate (4a)
Colorless crystals; mp 130-131 ˚C. IR (KBr): 2251 (CN), 1752 and 1724 (C=O) cm-¹. MS (EI): m/z (%) = 310 (100) [M+]. Anal. Calcd (%) for C17H14N2O4 (310.31): C, 65.80; H, 4.55; N, 9.03. Found: C, 65.7; H, 4.6; N, 8.9. ¹H NMR (500.1 MHz, CDCl3): δ = 3.61 (d, ² J = 17.3 Hz, 1 H, CH), 3.68 (s, 3 H, OCH3), 3.85 (dd, ² J = 17.3 Hz, 4 J = 1.6 Hz, 1 H, CH), 3.90 (s, 3 H, OCH3), 4.61 (br s, 1 H, CHCO2CH3), 7.37-7.45 (m, 5 H, 5 × CH). ¹³C NMR (125.8 MHz, CDCl3): δ = 34.50 [C(CN)2], 49.50 (CH2), 52.16 and 53.59 (2 × OCH3), 60.92 (CHCO2CH3), 113.21 and 115.27 (2 × CN), 124.41 (C), 128.09, 128.38 and 130.17 (3 × CH), 132.39 and 151.84 (2 × C), 162.85 and 167.64 (2 × C=O).
Diethyl 3-(4-Chlorophenyl)-5,5-dicyano-2-cyclopentene-1,2-dicarboxylate (4h)
Colorless crystals; mp 97-99 ˚C. IR (KBr): 2255 (CN), 1735 and 1715 (shoulder; C=O) cm-¹. MS (EI): m/z (%) = 374 (30) [M+ ³7Cl], 372 (100) [M+ ³5Cl]. Anal. Calcd (%) for C19H17ClN2O4 (372.81): C, 61.21; H, 4.60; N, 7.51. Found: C, 61.2; H, 4.6; N, 7.4. ¹H NMR (500.1 MHz, CDCl3): δ = 1.17 (t, J = 7.1 Hz, 3 H, CH2CH 3), 1.37 (t, J = 7.1 Hz, 3 H, CH2CH 3), 3.57 (d, ² J = 17.3 Hz, 1 H, CH), 3.80 (dd, ² J = 17.3 Hz, 4 J = 1.5 Hz, 1 H, CH), 4.12 and 4.17 [2 × dq, ABX3 system, ² J = 11.0 Hz, ³ J = 7.1 Hz, 2 H, OCH A H BCH3], 4.31 and 4.36 [2 × dq, ABX3 system, ² J = 10.7 Hz, ³ J = 7.2 Hz, 2 H, OCH A H BCH3], 4.56 (s, 1 H, CHCO2C2H5), 7.35 (d, J = 8.7 Hz, 2 H, 2 × CH), 7.38 (d, J = 8.7 Hz, 2 H, 2 × CH). ¹³C NMR (125.8 MHz, CDCl3): δ = 13.83 and 14.07 (2 × OCH2 CH3), 34.44 [C(CN)2], 49.32 (CH2), 60.74 (CHCO2C2H5), 61.50 and 63.5 (2 × OCH2CH3), 113.06 and 115.27 (2 × CN), 125.61 (C), 128.59 and 129.61 (2 × CH), 130.85, 136.16 and 150.14 (3 × C), 162.15 and 167.11 (2 × C=O).