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Experimental Procedure for Compound 3a.
Into a two-necked 3 mL flask were added (2-furyl)C(O)SPh (1a, 204.3 mg, 1.0 mmol), Pt(PPh3)4 (62.2 mg, 0.05 mmol), toluene (0.5 mL) and 1-octyne (2a, 132.2 mg, 1.2 mmol). After the solution was vigorously refluxed for 24 h, the resultant reaction mixture was separated by preparative TLC (PTLC) using pentane as an eluent to give the desired (Z)-1-(2-furyl)-2-(SPh)-1-hexene (3a) in 78% (223.4 mg) yield as a yellow oil. The stereo- and regiochemistry was determined by NOE and 13C-13C NMR measurement. Data of 3a: 1H NMR (400 MHz, CDCl3): δ = 7.42-7.39 (m, 3 H), 7.33-7.24 (m, 3 H), 6.87 (d, J = 3.2 Hz, 1 H), 6.62 (s, 1 H), 6.44-6.43 (m, 1 H), 2.25 (t, J = 7.4 Hz, 2 H), 1.55-1.48 (m, 2 H), 1.26-1.19 (m, 6 H), 0.86 (t, J = 7.0 Hz, 3 H). NOE experiment: irradiation at the methylene triplet at δ = 2.25 ppm resulted in a 7.8% enhancement at δ = 6.87 ppm (vinyl singlet). 13C NMR (100 MHz, CDCl3): δ = 151.7, 140.8, 134.6, 133.0, 131.7, 128.7, 127.0, 119.2, 111.4, 109.8, 37.7, 31.6, 29.0, 28.6, 22.6, 14.2. IR (neat): 3146, 3117, 3059, 3018, 2928, 2856, 2232, 1947, 1879, 1728, 1614, 1583, 1538, 1486, 1477, 1440, 1379, 1324, 1302, 1269, 1238, 1177, 1150, 1116, 1086, 1068, 1017, 943, 885, 802, 735, 704, 692 cm-1. MS (EI): m/e (%) = 286 (100) [M+]. Anal. Calcd for C18H22OS: C, 75.48; H, 7.74; S, 11.19. Found: C, 75.32; H, 7.68; S, 11.14.
13 Into a two-necked 3 mL flask were added Pt(PPh3)4 (37.3 mg, 0.03 mmol), thioester 1d (282.0 mg, 1.0 mmol), diethynylbenzene 2g (63.1 mg, 0.5 mmol) and toluene (0.5 mL). The reaction mixture was vigorously refluxed for 24 h under a nitrogen atmosphere and cooled to r.t. After the resultant mixture was filtrated through Celite, the product was reprecipitated from CH2Cl2 solution with pentane (isolated yield 70% based on 2g). Yellow solid: 1H NMR (400 MHz, CDCl3): δ = 7.50-7.19 (m, 14 H), 7.09-7.06 (m, 4 H), 6.89-6.86 (m, 4 H), 2.31 (s, 3 H), 2.21 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 154.0, 149.3, 140.1, 135.6, 131.6, 130.1, 129.5, 129.1, 127.9, 124.8, 122.3, 119.0, 118.7, 116.5, 111.1, 21.2, 9.1. MS (EI): m/e (%) = 634 (100) [M+]. UV: λmax = 387 nm. Anal. Calcd for C42H34O2S2: C, 79.46; H, 5.40. Found: C, 78.27; H, 5.39.
