Synlett 2007(16): 2521-2524  
DOI: 10.1055/s-2007-986663
LETTER
© Georg Thieme Verlag Stuttgart · New York

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;
Further Information

Publication History

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

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.

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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.