Ligand- and Base-Free Synthesis of 1,3-Diynes Catalyzed by Low Loading of Heterogeneous Pd/C and CuI

Takanori Kurita; Masami Abe; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

doi:10.1055/s-2007-986663

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Synlett 2007(16): 2521-2524
DOI: 10.1055/s-2007-986663

LETTER

Ligand- and Base-Free Synthesis of 1,3-Diynes Catalyzed by Low Loading of Heterogeneous Pd/C and CuI

Takanori Kurita, Masami Abe, Tomohiro Maegawa, Yasunari Monguchi, Hironao Sajiki*
Laboratory of Medicinal Chemistry, Gifu Pharmaceutical University, 5-6-1 Mitahora-higashi, Gifu 502-8585, Japan
Fax: +81(58)2375979; e-Mail: sajiki@gifu-pu.ac.jp;

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Publication History

Received 9 July 2007
Publication Date:
12 September 2007 (online)

Abstract
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Abstract

A facile and environmentally friendly synthetic method for a variety of symmetrical 1,3-diyne derivatives based on the Pd/C-CuI-catalyzed homocoupling reaction of terminal alkynes has been developed. The reaction was efficiently catalyzed by the extremely low loading (0.01-0.03 mol%) of Pd/C and CuI (3 mol%) in the presence of molecular oxygen (O₂) as an oxidant without any phosphine ligands and bases.

Key words

terminal alkynes - homocoupling - heterogeneous palladium on carbon - ligand- and base-free - oxygen

References and Notes

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19

General Procedure for Homocoupling Reaction of Terminal Alkynes:
To a test tube with a stir bar were added terminal alkyne (1 mmol), 1% Pd/C (1.1 mg, 0.01 mol%) for aromatic terminal alkyne or 3.2 mg, 0.03 mol% for aliphatic terminal alkyne; purchased from Sigma-Aldrich Co.), copper(I) iodide (5.7 mg, 3 mol%) and DMSO (0.5 mL) and the system was sealed with a septum. The air inside the test tube was replaced with oxygen (balloon) by five vacuum-oxygen cycles and the mixture was stirred at r.t. After 24 h, the mixture was diluted with H₂O (10 mL) and Et₂O (40 mL), and passed through a membrane filter (Millipore, Millex^®-LH, 0.45 µm). The filtrate was separated into two layers and the ethereal layer was washed subsequently with H₂O (70 mL) and brine (20 mL), dried over MgSO₄, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (hexane or hexane-Et₂O) to give the corresponding 1,3-diyne.
1,4-Bis(2-trifluoromethylphenyl)buta-1,3-diyne (5b): colorless solid; mp 70.8-71.7 °C. ¹H NMR: δ = 7.47 (t, J = 7.2 Hz, 2 H), 7.53 (t, J = 7.2 Hz, 2 H), 7.68 (d, J = 7.2 Hz, 2 H), 7.70 (d, J = 7.2 Hz, 2 H). ¹³C NMR: δ = 78.6, 78.7, 119.8 (q, J = 2.5 Hz), 123.3 (q, J = 273.4 Hz), 126.1 (q, J = 4.9 Hz), 129.2, 131.5, 132.6 (q, J = 30.9 Hz), 135.2. MS (EI): m/z (%) = 338 (100) [M⁺], 319 (18), 287 (11), 269 (27). HRMS (EI): m/z [M⁺] calcd for C₁₈H₈F₆: 338.0530; found: 338.0524. Anal. Calcd for C₁₈H₈F₆: C, 63.92; H, 2.38. Found: C, 64.03; H, 2.57.
1,4-Bis(3,5-ditrifluoromethylphenyl)buta-1,3-diyne (6b): colorless solid; mp 158.7-161.0 °C. ¹H NMR: δ = 7.89 (s, 2 H), 7.97 (s, 4 H). ¹³C NMR: δ = 76.1, 79.7, 122.7 (q, J = 272.8 Hz), 123.1 (sept, J = 3.7 Hz), 123.6, 132.4 (q, J = 34.1 Hz), 132.5 (q, J = 3.3 Hz). MS (EI): m/z (%) = 474 (100) [M⁺], 455 (17), 405 (9). HRMS (EI): m/z [M⁺] calcd for C₂₀H₆F₁₂: 474.0278; found: 474.0269. Anal. Calcd for C₂₀H₆F₁₂: C, 50.65; H, 1.28. Found: C, 50.55; H, 1.45.
1,10-Biscyanodeca-4,6-diyne (9b): yellow oil. ¹H NMR: δ = 1.90 (m, 4 H), 2.47 (t, J = 6.8 Hz, 4 H), 2.50 (t, J = 7.1 Hz, 4 H). ¹³C NMR: δ = 16.2, 18.3, 24.2, 66.8, 75.2, 118.8. MS (EI): m/z (%) = 184 (100) [M⁺], 119 (24), 105 (74), 91 (100). HRMS (EI): m/z [M⁺] calcd for C₁₂H₁₂N₂: 184.1001; found: 184.1009. Anal. Calcd for C₁₂H₁₂N₂·0.08H₂O: C, 77.62; H, 6.60; N, 15.09. Found: C, 77.67; H, 6.55; N, 14.99.
1,6-Bisbenzoyloxyhexa-2,4-diyne (11b): colorless solid. ¹H NMR: δ = 4.99 (s, 4 H), 7.45 (t, J = 7.6 Hz, 4 H), 7.58 (tt, J = 1.4, 7.6 Hz, 4 H), 8.06 (dt, J = 1.4, 7.6 Hz, 2 H). ¹³C NMR: δ = 52.7, 70.5, 73.8, 128.5, 129.2, 129.8, 133.4, 165.6. MS (EI): m/z (%) = 318 (9) [M⁺], 105 (100), 77 (18). HRMS (EI): m/z [M⁺] calcd for C₂₀H₁₄O₄: 318.0892; found: 318.0897. Anal. Calcd for C₂₀H₁₄O₄: C, 75.46; H, 4.43. Found: C, 75.56; H, 4.65.
1,6-Dimethyl-1,6-diphenylhexa-2,4-diyne-1,6-diol (12b): colorless solid; mp 146.5-148.5 °C. ¹H NMR: δ = 1.65 (s, 6 H), 6.34 (s, 2 H), 7.27 (t, J = 7.2 Hz, 2 H), 7.36 (t, J = 7.2 Hz, 4 H), 7.52 (d, J = 7.2 Hz, 4 H). ¹³C NMR: δ = 33.7, 67.8, 69.1, 85.6, 125.5, 128.1, 128.9, 146.3. MS (NBA, FAB): m/z (%) = 273 (59) [M - (OH)]⁺, 229 (7) [M - 2 × (OH) - 2 × (Me)]⁺. Anal. Calcd for C₂₀H₁₈O₂: C, 82.73; H, 6.25. Found: C, 82.55; H, 6.48.
1,6-Bisphenylthiohexa-2,4-diyne (14b): yellow oil. ¹H NMR: δ = 3.64 (s, 4 H), 7.24-7.27 (m, 2 H), 7.30-7.33 (m, 4 H), 7.42-7.44 (m, 4 H). ¹³C NMR: δ = 23.6, 67.9, 74.6, 127.3, 129.1, 130.5, 134.5. MS (EI): m/z (%) = 294 (20) [M⁺], 184 (100). HRMS (EI): m/z [M⁺] calcd for C₁₈H₁₄S₂: 294.0537; found: 294.0530. Anal. Calcd for C₁₈H₁₄S₂: C, 73.43; H, 4.79. Found: C, 73.39; H, 4.92.