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DOI: 10.1055/s-2006-951498
Alkylative Cyclization of 1,6-Enynes in Water with an Amphiphilic Resin-Supported Palladium Catalyst
Publication History
Publication Date:
25 October 2006 (online)
Abstract
An alkylative cyclization of a 1,6-enyne with aryl halides was performed with an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin supported phosphine-palladium complex in water under heterogeneous conditions to give benzylidenecyclohexenes in good to high yields, which proceeds via formation of a vinylpalladium intermediate and subsequent intramolecular Heck reaction. The polymeric palladium catalyst can be readily recovered and recycled.
Key words
cyclization - 1,6-enyne - aqueous media - polymer support - palladium catalyst
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References and Notes
TentaGel NH2 (Φ = 90 mm, loading value = 0.3 mmol/g) was used as a starting polymer support.
11
General Procedure for Alkylative Cyclization of 1,6-Enyne 1 with Aryl Halides.
A mixture of 1 (95 mg, 0.4 mmol), the aryl halide 2 (0.4 mmol), 5 mol% palladium of 4 (90 mg, 20 µmol Pd), 170 mg of NaHCO3 (2.0 µmol), and 4 µL of H2O was refluxed for 90 min. After it was cooled, the mixture was filtered and the collected resin beads were extracted by washing with EtOAc. The washing was concentrated in vacuo to give the alkylative cyclized product 3. An analytically pure product was isolated by silica gel chromatography. Spectroscopic data of new compounds are given below.
Diethyl (
Z
)-5-(Phenylmethylene)-3-cyclohexene-1,1-dicarboxylate (3a).
1H NMR (500 MHz, CDCl3): δ = 1.15 (t, J = 7.0 Hz, 6 H, CH3), 2.75 (dd, J = 1.8, 4.3 Hz, 2 H, CH=CHCH2), 3.16 (d, J = 1.2 Hz, 2 H, CH=CCH2), 4.08-4.19 (m, 4 H, OCH2), 5.83 (td, J = 4.3, 9.5 Hz, 1 H, CH=CHCH2), 6.21 (td, J = 1.8, 9.5 Hz, 1 H, CH=CHCH2), 6.41 (s, 1 H, ArCH=C), 7.20-7.23 (m, 1 H, ArH), 7.31-7.35 (m, 4 H, ArH). 13C NMR (125 MHz, CDCl3): δ = 13.9 (CH3), 31.2 (CH2), 31.5 (CH2), 54.0 (CH2CCH2), 61.5 (OCH2), 125.8 (CH=CHCH2), 126.6 (Ar), 128.2 (Ar), 128.89 (ArCH=C), 128.93 (Ar), 131.0 (CH=CHCH2), 132.9 (ArCH=C), 137.0 (Ar), 171.0 (C=O). MS: m/z = 314 [M+], 241, 211, 167. HRMS: m/z calcd for C19H22O4: 314.1518; found: 314.1507.
Diethyl (
Z
)-5-[(2-Methylphenyl)methylene]-3-cyclohexene-1,1-dicarboxylate (3b).
1H NMR (500 MHz, CDCl3): δ = 1.16 (t, J = 7.1 Hz, 6 H, CH2CH3), 2.23 (s, 3 H, CH3), 2.74 (dd, J = 1.5, 4.2 Hz, 2 H, CH=CHCH2), 2.98 (d, J = 1.8 Hz, 2 H, CH=CCH2), 4.12 (q, J = 7.1 Hz, 4 H, OCH2), 5.83 (td, J = 4.2, 9.5 Hz, 1 H, CH=CHCH2), 6.26 (td, J = 1.8, 9.5 Hz, 1 H, CH=CHCH2), 6.41 (s, 1 H, ArCH=C), 7.13-7.19 (m, 3 H, ArH), 7.25-7.27 (m, 1 H, ArH). 13C NMR (125 MHz, CDCl3): δ = 13.9 (CH2CH3), 19.9 (CH3), 31.39 (CH2), 31.41 (CH2), 54.0 (CH2CCH2), 61.4 (OCH2), 125.4 (CH=CHCH2), 125.6 (Ar), 126.9 (Ar), 127.9 (ArCH=C), 129.0 (Ar), 129.7 (Ar), 130.7 (CH=CHCH2), 132.8 (ArCH=C), 136.0 (Ar), 136.5 (Ar), 171.0 (C=O). MS: m/z = 328 [M+], 255, 225, 181, 165. HRMS: m/z calcd for C20H21F3O4: 382.1392; found: 382.1374.
Diethyl (
Z
)-5-[(3-Methylphenyl)methylene]-3-cyclohexene-1,1-dicarboxylate (3c).
1H NMR (500 MHz, CDCl3): δ = 1.16 (t, J = 6.7 Hz, 6 H, CH2CH3), 2.35 (s, 3 H, CH3), 2.75 (dd, J = 1.8, 4.5 Hz, 2 H, CH=CHCH2), 3.15 (d, J = 1.8 Hz, 2 H, CH=CCH2), 4.10-4.18 (m, 4 H, OCH2), 5.81 (td, J = 4.5, 9.5 Hz, 1 H, CH=CHCH2), 6.20 (d, J = 9.5 Hz, 1 H, CH=CHCH2), 6.37 (s, 1 H, ArCH=C), 7.03 (d, J = 7.7 Hz, 1 H, ArH), 7.11 (s, 1 H, ArH), 7.13 (d, J = 7.7 Hz, 1 H, ArH), 7.23 (t, J = 7.7 Hz, 1 H, ArH). 13C NMR (125 MHz, CDCl3): δ = 13.9 (CH2CH3), 21.4 (CH3), 31.2 (CH2), 31.5 (CH2), 54.0 (CH2CCH2), 61.4 (OCH2), 125.5 (Ar), 126.0 (CH=CHCH2), 127.4 (Ar), 128.0 (Ar), 129.0 (ArCH=C), 129.7 (Ar), 131.1 (CH=CHCH2), 132.8 (ArCH=C), 137.0 (Ar), 137.6 (Ar), 171.0 (C=O). MS: m/z = 328 [M+], 255, 225, 181, 165. HRMS: m/z calcd for C20H24O5: 344.1624; found: 344.1620.
Diethyl (
Z
)-5-[(4-Methylphenyl)methylene]-3-cyclohexene-1,1-dicarboxylate (3d).
1H NMR (500 MHz, CDCl3): δ = 1.15 (t, J = 7.0 Hz, 6 H, CH2CH3), 2.34 (s, 3 H, CH3), 2.74 (dd, J = 1.8, 4.5 Hz, 2 H, CH=CHCH2), 3.15 (d, J = 1.8 Hz, 2 H, CH=CCH2), 4.08-4.18 (m, 4 H, OCH2), 5.80 (td, J = 4.5, 9.8 Hz, 1 H, CH=CHCH2), 6.20 (d, J = 9.8 Hz, 1 H, CH=CHCH2), 6.37 (s, 1 H, ArCH=C), 7.14 (d, J = 7.9 Hz, 2 H, ArH), 7.21 (d, J = 7.9 Hz, 2 H, ArH). 13C NMR (125 MHz, CDCl3): δ = 13.9 (CH2CH3), 21.2 (CH3), 31.2 (CH2), 31.5 (CH2), 53.9 (CH2CCH2), 61.4 (OCH2), 125.3 (CH=CHCH2), 128.85, 128.87 (3 C, 2 Ar, ArCH=C), 131.1 (CH=CHCH2), 132.3 (ArCH=C), 134.2 (Ar), 136.3 (Ar), 171.0 (C=O). MS: m/z = 328 [M+], 255, 225, 181, 165. HRMS: m/z calcd for C20H24O4: 328.1675; found: 328.1673.
Diethyl (
Z
)-5-[(4-Methoxyphenyl)methylene]-3-cyclohexene-1,1-dicarboxylate (3e).
1H NMR (500 MHz, CDCl3): δ = 1.16 (t, J = 7.3 Hz, 6 H, CH2CH3), 2.74 (dd, J = 1.8, 4.3 Hz, 2 H, CH=CHCH2), 3.14 (d, J = 1.8 Hz, 2 H, CH=CCH2), 3.82 (s, 3 H, OCH3), 4.08-4.19 (m, 4 H, OCH2), 5.78 (td, J = 4.3, 9.5 Hz, 1 H, CH=CHCH2), 6.19 (td, J = 1.8, 9.5 Hz, 1 H, CH=CHCH2), 6.34 (s, 1 H, ArCH=C), 6.88 (d, J = 8.6 Hz, 2 H, ArH), 7.26 (d, J = 8.6 Hz, 2 H, ArH). 13C NMR (125 MHz, CDCl3): δ = 13.9 (CH2CH3), 31.2 (CH2), 31.5 (CH2), 53.9 (CH2CCH2), 55.2 (OCH3), 61.4 (OCH2), 113.7 (Ar), 124.9 (CH=CHCH2), 128.5 (ArCH=C), 129.7 (Ar), 130.2 (Ar), 131.2 (CH=CHCH2), 131.5 (ArCH=C), 158.3 (Ar), 171.0 (C=O). MS: m/z = 344 [M+], 270, 241, 197. HRMS: m/z calcd for C20H24O4: 328.1675; found: 328.1689.
Diethyl (
Z
)-5-[(4-Trifluoromethylphenyl)methylene]-3-cyclohexene-1,1-dicarboxylate (3f).
1H NMR (500 MHz, CDCl3): δ = 1.16 (t, J = 7.0 Hz, 6 H, CH3), 2.78 (dd, J = 1.5, 4.0 Hz, 2 H, CH=CHCH2), 3.12 (d, J = 1.8 Hz, 2 H, CH=CCH2), 4.09-4.19 (m, 4 H, OCH2), 5.90 (td, J = 4.0, 9.3 Hz, 1 H, CH=CHCH2), 6.22 (td, J = 1.8, 9.3 Hz, 1 H, CH=CHCH2), 6.41 (s, 1 H, ArCH=C), 7.42 (d, J = 8.5 Hz, 2 H, ArH), 7.59 (d, J = 8.5 Hz, 2 H, ArH). 13C NMR (125 MHz, CDCl3): δ = 13.9 (CH3), 31.3 (CH2), 31.5 (CH2), 53.9 (CH2CCH2), 61.6 (OCH2), 125.2 (2 C, q, 2
J
C-F = 3.8 Hz, 2 Ar), 127.26 (CH=CHCH2 or ArCH=C), 127.31 (CH=CHCH2 or ArCH=C), 128.5 (q, 1
J
C-F = 32.4 Hz, CF3), 129.1 (Ar), 130.7 (CH=CHCH2), 135.0 (ArCH=C), 140.7 (Ar), 171.0 (C=O). MS: m/z = 382 [M+], 363, 309, 279, 235, 165. HRMS: m/z calcd for C20H24O4: 328.1675; found: 328.1688.