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DOI: 10.1055/s-0030-1258994
An Efficient Multicomponent Synthesis of Highly Functionalized Cyclopentenes
Publication History
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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References and Notes
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).