Palladium-Catalyzed Self-Coupling Reaction of Terminal Alkynes in the Presence of p-Chloranil: A Practical Method for the Synthesis of Triethynylethenes

Abstract

Pd-catalyzed reaction of aliphatic-1-alkynes in the presence of p-chloranil afforded triethynylethenes as exclusive self-coupling products in good yields. On the other hand, diynes were obtained when aromatic alkynes were used.

Key words

coupling reaction - alkyne - quinone - triethynylethene - palladium catalyst

References and Notes

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14

Typical Reaction Procedure and Spectroscopic Data: To a solution of Pd(PPh₃)₄ (40 mg, 3.5 mmol%), CuCl (2 mg, 0.5 mmol%), 1-heptyne (525 µL, 4.0 mmol) in THF (6 mL), p-chloranil (1.0 mmol) and Et₃N (2.6 mmol, 0.4 mL) were added under a N₂ atmosphere. The mixture was allowed to stir at r.t. for 12 h, and quenched with 3 N HCl. The resulting solution was extracted with Et₂O and washed with a sat. NaCl solution. The combined Et₂O fractions were dried over Na₂SO₄ and concentrated under vacuum to yield the crude product. The crude product was purified by flash chromatography on silica gel using PE as the eluent. Removal of the solvent yielded 3a (342 mg) as a colorless liquid (90% isolated yield).
8-(Hept-1-ynyl)-9-pentylhexadeca-8-en-6,10-diyne (3a)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.88-0.93 (m, 12 H), 1.28-1.47 (m, 16 H), 1.51-1.62 (m, 8 H), 2.34-2.44 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 14.0, 19.7, 19.7, 20.0, 22.3, 22.5, 27.9, 28.4, 28.5, 28.6, 31.1, 31.4, 34.6, 77.8, 79.3, 81.0, 92.5, 96.9, 100.9, 109.3, 138.1. GC-MS: m/z = 380. HRMS: m/z calcd for C₂₈H₄₄: 380.3443; found: 380.3441.
9-Hexyl-10-(oct-1-ynyl)octadeca-9-en-7,11-diyne (3b)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.85-0.89 (m, 12 H), 1.28 (d, J = 2.7 Hz, 16 H), 1.34-1.59 (m, 16 H), 2.33-2.42 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 14.0, 19.7, 20.0, 22.5, 28.1, 28.5, 28.7, 28.7, 28. 8, 31.3, 31.4, 31.7, 34.6, 77.6, 79.1, 80.8, 92.5, 96.9, 100.9, 109.1, 138.1. GC-MS: m/z = 436. HRMS: m/z calcd for C₃₂H₅₂: 436.4069; found: 436.4071.
7-Butyl-8-(hex-1-ynyl)tetradeca-7-en-5,9-diyne (3c)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.86-0.93 (m, 12 H), 1.24-1.59 (m, 16 H), 2.34-2.43 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 13.5, 13.5, 13.6, 13.8, 19.30, 19.4, 21.9, 22.2, 30.3, 30.6, 30.7, 30.8, 34.3, 77.7, 79.2, 80.9, 92.3, 96.8, 100.8, 109.1, 138.0. GC-MS: m/z = 324. HRMS: m/z calcd for C₂₄H₃₆: 324.2817; found: 324.2815.
6-(Pent-1-ynyl)-7-propyldodeca-6-en-4,8-diyne (3d) ¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.91 (t, J = 7.2 Hz, 3 H), 1.00 (q, J = 7.2 Hz, 9 H), 1.49-1.63 (m, 8 H), 2.31-2.41 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 13.4, 13.6, 21.5, 21.6, 21.7, 22.0, 36.6, 77.8, 79.3, 81.0, 92.3, 96.8, 100.7, 109.2, 137.9. GC-MS: m/z = 268. HRMS: m/z calcd for C₂₀H₂₈: 268.2191; found: 268.2194.
5-Phenethyl-1,10-diphenyl-6-(4-phenylbut-1-ynyl)deca-5-en-3,7-diyne (3e)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 7.08-7.28 (m, 20 H), 2.57-2.90 (m, 16 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 22.0, 22.0, 22.3, 34.4, 35.0, 35.2, 35.2, 36.5, 78.1, 79.6, 81.4, 92.4, 96.8, 100.9, 109.7, 126.0, 126.3, 126.4, 128.3, 128.4, 128.5, 128.5, 137.2, 140.5, 140.6, 140.7, 141.5. HRMS: m/z calcd for C₄₀H₃₆: 516.2817; found: 516.2820.
1,12-Dichloro-6-(5-chloropent-1-ynyl)-7-(3-chloro-propyl)dodeca-6-en-4,8-diyne (3f)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 1.95-2.08 (m, 8 H), 2.52-2.68 (m, 8 H), 3.52-3.75 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 17.0, 17.2, 17.4, 31.2, 31.3, 31.8, 43.6, 43.6, 43.7, 44.3, 77.9, 79.7, 81.2, 91.2, 96.1, 99.7, 110.2, 136.5. GC-MS: m/z = 408. HRMS: m/z calcd for C₂₀H₂₄Cl₄: 404.0632; found: 404.0636.