1516
Krausová et al.:
(–)-Triisopropyl[4-(1-{[4-m eth oxy-2-({[(1S)-1-m eth yl-3-(4-m eth ylph en yl)-
2-propyn yl]oxy}m eth yl)ph en yl]eth yn yl}-2-n aph th yl)-1-butyn yl]silan e (26)
A Sch len k flask was ch arged with iodide (–)-(S)-24 (528 m g, 1.30 m m ol), [Pd(PPh 3)4] (68 m g,
58.8 µm ol, 5 m ole %) an d CuI (21 m g, 0.112 m m ol, 9 m ole %) an d filled with argon . A so-
lution of diyn e 25 (517 m g, 1.43 m m ol, 1.10 equiv.) in diisopropylam in e (13 m l) was added
an d th e reaction m ixture was stirred at 80 °C for 10 m in . After coolin g to room tem perature,
th e reaction m ixture was filtered th rough sin tered glass an d th e solid residue was wash ed
with a m ixture of petroleum eth er–eth er (99:1). Solven ts were rem oved in vacuo an d th e
crude product was ch rom atograph ed on silica gel (petroleum eth er–eth er, 95:5) to provide
triyn e (–)-(S)-26 (755 m g, 91%) as an oil. 1H NMR (500 MHz, CDCl3): 0.89–1.04 (21 H, m ),
1.61 (3 H, d, J = 6.6), 2.29 (3 H, s), 2.73 (2 H, t, J = 7.4), 3.27 (2 H, t, J = 7.4), 3.87 (3 H, s),
4.58 (1 H, q, J = 6.6), 4.99 (1 H, d, J = 12.9), 5.16 (1 H, d, J = 12.9), 6.85 (1 H, dd, J = 8.5,
2.7), 6.97 (2 H, m ), 7.17 (1 H, d, J = 2.7), 7.22 (2 H, m ), 7.42 (1 H, ddd, J = 8.1, 6.8, 1.4),
7.44 (1 H, d, J = 8.4), 7.47 (1 H, ddd, J = 8.4, 6.8, 1.4), 7.59 (1 H, d, J = 8.5), 7.72 (1 H, bd,
J = 8.4), 7.80 (1 H, ddt, J = 8.1, 1.4, 0.7, 0.7), 8.45 (1 H, ddt, J = 8.4, 1.4, 0.8, 0.8). 13C NMR
(125 MHz, CDCl3): 11.32 (d), 18.60 (q), 21.12 (t), 21.40 (q), 22.33 (q), 34.90 (t), 55.42 (q),
65.75 (d), 68.96 (t), 81.13 (s), 85.62 (s), 88.23 (s), 89.20 (s), 96.61 (s), 108.19 (s), 112.96 (d),
113.38 (d), 114.21 (s), 119.58 (s), 119.72 (s), 125.65 (d), 126.22 (d), 126.73 (d), 127.55 (d),
127.88 (d), 127.96 (d), 128.87 (d), 131.61 (d), 132.03 (s), 133.52 (s), 133.73 (d), 138.28 (s),
141.28 (s), 141.72 (s), 160.03 (s). IR (CHCl3): 3058 w, 2989 m , 2866 vs, 2225 w, 2201 w,
2170 m , 1620 w (sh ), 1606 s, 1592 w (sh ), 1566 m , 1510 s, 1498 s, 1465 s, 1445 m , 1430 w,
1420 w (sh ), 1390 w (sh ), 1383 w, 1373 w, 1368 w (sh ), 1328 m , 1315 m (sh ), 1296 m ,
1279 m , 1259 m , 1234 m , 1192 w, 1163 m , 1130 w (sh ), 1117 m , 1107 m (sh ), 1094 m ,
1059 m , 1035 m , 1025 m , 996 w, 920 w, 884 m , 866 w, 819 s, 678 m , 660 m , 616 w, 599 w (sh),
524 w, 440 w, 408 w. EI MS: 638 (M• +) (8), 595 (3), 565 (5), 495 (11), 465 (4), 429 (8),
321 (13), 239 (10), 173 (13), 159 (21), 143 (100), 129 (41), 115 (49), 87 (32), 73 (42), 59 (36).
HR EI MS: calculated for C44H50O2Si 638.3580; foun d 638.3567. α 2D2 –72 (c 0.15, CH2Cl2).
(–)-Triisopropyl[4-(7-m eth oxy-1-{[2-({[(1S)-1-m eth yl-3-(4-m eth ylph en yl)-
2-propyn yl]oxy}m eth yl)-1-n aph th yl]eth yn yl}-2-n aph th yl)-1-butyn yl]silan e (29)
A Sch len k flask was ch arged with iodide (–)-(S)-27 (95 m g, 0.223 m m ol), [Pd(PPh 3)4] (14 m g,
12.1 µm ol, 5 m ole %) an d CuI (4 m g, 21.0 µm ol, 9 m ole %) an d filled with argon .
Diisopropylam in e (3 m l) was added an d th e resultin g solution was stirred at room tem pera-
ture for 5 m in . A solution of diyn e 28 (95 m g, 0.243 m m ol, 1.09 equiv.) in diisopropyl-
am in e (4 m l) was added an d th e reaction was stirred at room tem perature for 2 h . Solven t
was rem oved in vacuo an d th e crude product was ch rom atograph ed on silica gel (petroleum
eth er–eth er, 100:0 to 95:5) to provide triyn e (–)-(S)-29 (67 m g, 44%). 1H NMR (500 MHz,
CDCl3): 0.94–1.01 (21 H, m ), 1.59 (3 H, d, J = 6.6), 2.26 (3 H, s), 2.78 (2 H, t, J = 7.2),
3.37 (2 H, dt, J = 7.2, 7.2, 2.3), 3.97 (3 H, s), 4.57 (1 H, q, J = 6.6), 5.30 (1 H, d, J = 12.7),
5.37 (1 H, d, J = 12.7), 6.88 (2 H, m ), 7.12 (2 H, m ), 7.14 (1 H, dd, J = 8.8, 2.6), 7.36 (1 H, d,
J = 8.3), 7.53 (1 H, ddd, J = 8.1, 6.8, 1.2), 7.59 (1 H, ddd, J = 8.4, 6.8, 1.4), 7.70 (1 H, bd, J =
8.3), 7.73 (1 H, d, J = 8.8), 7.78 (1 H, d, J = 8.5), 7.89 (1 H, bd, J = 8.5), 7.89 (1 H, ddt, J =
8.1, 1.4, 0.7, 0.7), 7.93 (1 H, d, J = 2.6), 8.68 (1 H, ddt, J = 8.4, 1.2, 0.9, 0.9). 13C NMR
(125 MHz, CDCl3): 11.29 (d), 18.57 (q), 21.36 (t), 21.38 (q), 22.37 (q), 34.94 (t), 55.46 (q),
65.55 (d), 69.23 (t), 81.32 (s), 85.71 (s), 88.27 (s), 94.20 (s), 96.46 (s), 104.53 (d), 107.97 (s),
118.23 (s), 118.71 (d), 119.36 (s), 119.42 (s), 125.41 (d), 125.60 (d), 126.22 (d), 126.24 (d),
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 11, pp. 1499–1522