Alkylative Cyclization of 1,6-Enynes in Water with an Amphiphilic Resin-Supported Palladium Catalyst

Yasushi Nakai; Tsutomu Kimura; Yasuhiro Uozumi

doi:10.1055/s-2006-951498

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Synlett 2006(18): 3065-3068
DOI: 10.1055/s-2006-951498

LETTER

Alkylative Cyclization of 1,6-Enynes in Water with an Amphiphilic Resin-Supported Palladium Catalyst

Yasushi Nakai, Tsutomu Kimura, Yasuhiro Uozumi*
Institute for Molecular Science, The Graduate University for Advanced Studies, CREST, Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
Fax: +81(564)595574; e-Mail: uo@ims.ac.jp;

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Publication History

Received 11 April 2006
Publication Date:
25 October 2006 (online)

Abstract
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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

References and Notes

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9

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.