L. Zhang et al. / Tetrahedron 62 (2006) 11371–11380
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13C NMR (125 MHz, CDCl3) d 141.5, 128.4, 128.2, 125.9,
87.2, 36.4, 29.9, 19.3, 17.3, 11.8; IR (neat, cmꢀ1) 3296,
2945, 2868, 2279, 1603, 1454; MS (APCI) calculated for
[C19H31OSi]+: 303.21; found: 303.1.
7.2.8. Siloxy alkyne 1h. 1H NMR (500 MHz, CDCl3) d 7.38
(d, 2H, J¼7.5 Hz), 7.31 (dd, 2H, J¼6.0, 7.5 Hz), 7.25 (t, 1H,
J¼6.0 Hz), 5.29 (d, 1H, J¼1.5 Hz), 5.12 (d, 1H, J¼1.5 Hz),
2.63 (dd, 1H, J¼7.0, 9.0 Hz), 2.57 (dd, 1H, J¼6.5, 9.0 Hz),
2.35 (m, 1H), 1.53 (m, 1H), 1.43–1.23 (m, 6H), 1.12 (d, 18H,
J¼7.5 Hz), 0.85 (t, 3H, J¼7.0 Hz); 13C NMR (125 MHz,
CDCl3) d 146.7, 141.2, 128.2, 127.2, 126.3, 114.0,
88.2, 42.6, 37.9, 33.6, 28.8, 20.4, 17.4, 14.0, 11.8; IR
(neat, cmꢀ1) 3082, 2947, 2868, 2273, 2076, 1628, 1464,
1385; MS (APCI) calculated for [C24H39OSi]+: 371.28;
found: 371.2.
7.2.2. Siloxy alkyne 1b. 1H NMR (500 MHz, CDCl3)
d 7.82–7.72 (m, 3H), 7.66 (s, 1H), 7.47–7.41 (m, 2H), 7.37
(d, 1H, J¼8.5 Hz), 2.93 (t, 2H, J¼7.5 Hz), 2.51 (t, 2H,
J¼7.5 Hz), 1.15 (h, 3H, J¼7.5 Hz), 1.04 (d, 18H,
J¼7.5 Hz); 13C NMR (125 MHz, CDCl3) d 138.9, 133.5,
132.1, 127.7, 127.5, 127.4, 127.2, 126.6, 125.1, 87.4, 36.4,
29.8, 19.2, 18.0, 17.3, 11.7; IR (neat, cmꢀ1) 2945, 2867,
2278, 1463; MS (APCI) calculated for [C23H33OSi]+:
353.23; found: 353.2.
7.2.9. Siloxy alkyne 1i. 1H NMR (500 MHz, CDCl3) d 5.23
(q, 1H, J¼5.5 Hz), 2.40 (m, 1H), 2.04 (m, 2H), 1.58–1.51
(m, 7H), 1.36–1.32 (m, 3H), 1.28–1.21 (m, 3H), 1.11 (d,
18H, J¼7.5 Hz), 0.88 (t, 3H, J¼7.5 Hz); 13C NMR
(125 MHz, CDCl3) d 134.1, 120.0, 88.0, 46.8, 38.0, 33.9,
7.2.3. Siloxy alkyne 1c. 1H NMR (500 MHz, CDCl3)
d 7.31–7.17 (m, 5H), 2.69 (d, 2H, J¼7.0 Hz), 2.56
(m, 1H), 1.57 (m, 1H), 1.44–1.30 (m, 3H), 1.20 (h, 3H,
J¼7.5 Hz), 1.09 (d, 18H, J¼7.5 Hz), 0.89 (t, 3H, J¼
7.0 Hz); 13C NMR (125 MHz, CDCl3) d 140.7, 129.2,
127.9, 125.7, 88.5, 42.8, 37.8, 33.5, 32.2, 20.5, 17.3, 13.9,
11.7; IR (neat, cmꢀ1) 3063, 3027, 2946, 2868, 2273, 2077,
1604, 1464; MS (APCI) calculated for [C22H37OSi]+:
345.26; found: 345.2.
28.6, 20.5, 17.3, 15.4, 14.0, 13.3, 11.8; IR (neat, cmꢀ1
)
2947, 2869, 2273, 2077, 1602, 1464; MS (APCI) calculated
for [C20H39OSi]+: 323.28; found: 323.2.
7.2.10. Siloxy alkyne 1j. 1H NMR (500 MHz, CDCl3) d 5.42
(s, 1H), 2.38 (m, 1H), 2.05–1.83 (m, 6H), 1.60–1.50 (m, 5H),
1.41–1.37 (m, 2H), 1.23 (h, 3H, J¼7.5 Hz), 1.11 (d, 18H,
J¼7.5 Hz), 0.88 (t, 3H, J¼7.2 Hz); 13C NMR (125 MHz,
CDCl3) d 136.0, 122.5, 87.8, 45.3, 38.1, 33.9, 28.3, 28.1,
7.2.4. Siloxy alkyne 1d. 1H NMR (500 MHz, CDCl3) d 7.19
(t, 1H, J¼8.0 Hz), 6.80 (d, 1H, J¼8.0 Hz), 6.76 (s, 1H), 6.74
(d, 1H, J¼8.0 Hz), 3.80 (s, 3H), 2.74 (t, 2H, J¼7.5 Hz), 2.39
(t, 2H, J¼7.5 Hz), 1.19 (h, 3H, J¼7.5 Hz), 1.09 (d, 18H,
J¼7.5 Hz); 13C NMR (125 MHz, CDCl3) d 159.5, 143.1,
129.1, 120.8, 114.2, 111.2, 87.2, 55.1, 36.5, 29.9, 19.2,
17.3, 11.7; IR (neat, cmꢀ1) 2946, 2868, 2279, 1602, 1585,
1490; MS (APCI) calculated for [C20H33O2Si]+: 333.22;
found: 333.2.
25.3, 23.0, 22.5, 20.5, 17.4, 14.0, 11.7; IR (neat, cmꢀ1
)
2929, 2868, 2273, 1607, 1464; MS (APCI) calculated for
[C22H40OSi]+: 349.29; found: 349.5.
7.2.11. Siloxy alkyne 1k. 1H NMR (500 MHz, CDCl3)
d 2.30–2.24 (m, 4H), 2.14–2.11 (m, 2H), 1.51–1.44 (m,
2H), 1.34–1.22 (m, 13H), 1.13–1.12 (d, 18H, J¼7.5 Hz),
0.88 (t, 3H, J¼6.8 Hz); 13C NMR (125 MHz, CDCl3)
d 87.3, 80.7, 79.2, 31.9, 29.5, 29.2, 29.1, 29.1, 28.9, 22.7,
20.4, 18.7, 18.2, 17.3, 14.1, 11.8; IR (neat, cmꢀ1) 2928,
2868, 2361, 2281; MS (APCI) calculated for [C23H43OSi]+:
363.31; found: 363.3.
7.2.5. Siloxy alkyne 1e. 1H NMR (500 MHz, CDCl3) d 7.38
(d, 2H, J¼8.5 Hz), 7.08 (d, 2H, J¼8.5 Hz), 2.69 (t, 2H,
J¼7.5 Hz), 2.37 (t, 2H, J¼ 7.5 Hz), 1.17 (h, 3H,
J¼7.0 Hz), 1.06 (d, 18H, J¼7.0 Hz); 13C NMR (125 MHz,
CDCl3) d 140.4, 131.2, 130.3, 119.7, 87.5, 35.6, 29.4,
19.1, 17.3, 11.7; IR (neat, cmꢀ1) 2945, 2867, 2279, 1592,
1488, 1463; MS (APCI) calculated for [C19H30BrOSi]+:
381.12; found: 381.1.
7.2.12. Siloxy alkyne 1l. 1H NMR (500 MHz, CDCl3)
d 7.33–7.29 (m, 2H), 7.24–7.21 (m, 3H), 2.82 (t, 2H,
J¼7.5 Hz), 2.46–2.42 (m, 2H), 2.31–2.26 (m, 4H), 1.32–
1.24 (m, 3H), 1.15 (d, 18H, J¼4.0 Hz); 13C NMR
(125 MHz, CDCl3) d 141.0, 128.4, 128.3, 126.1, 87.4,
80.1, 80.0, 35.5, 29.4, 21.0, 20.3, 18.1, 17.3, 11.8; IR
(neat, cmꢀ1) 3028, 2945, 2868, 2280, 1604; MS (APCI)
calculated for [C23H35OSi]+: 355.25; found: 355.2.
7.2.6. Siloxy alkyne 1f. 1H NMR (500 MHz, CDCl3) d 4.74
(s, 1H), 4.71 (s, 1H), 2.43 (m, 1H), 2.13–2.05 (m, 2H), 1.71
(s, 3H), 1.54 (m, 1H), 1.42–1.31 (m, 3H), 1.25 (h, 3H,
J¼7.5 Hz), 1.11 (d, 18H, J¼7.5 Hz), 0.89 (t, 3H, J¼
7.2 Hz); 13C NMR (125 MHz, CDCl3) d 144.1, 111.6,
88.0, 44.9, 38.0, 33.6, 28.5, 22.2, 20.5, 17.4, 13.9, 11.8;
IR (neat, cmꢀ1) 2947, 2869, 2274, 2078, 1649, 1464;
MS (APCI) calculated for [C19H37OSi]+: 309.26; found:
309.2.
1
7.2.13. Siloxy alkyne 1m. H NMR (500 MHz, CDCl3)
d 7.32–7.27 (m, 2H), 7.23–7.19 (m, 3H), 2.74 (t, 2H,
J¼7.8 Hz), 2.35–2.29 (m, 4H), 2.20–2.17 (m, 2H), 1.85–
1.79 (m, 2H), 1.34–1.25 (m, 3H), 1.15 (d, 18H, J¼7.5 Hz);
13C NMR (125 MHz, CDCl3) d 141.8, 128.5, 128.2, 125.7,
87.4, 80.2, 79.9, 34.8, 30.6, 29.4, 20.4, 18.2, 18.0, 17.3,
11.8; IR (neat, cmꢀ1) 2945, 2868, 2280, 1604, 1463; MS
(APCI) calculated for [C24H37OSi]+: 369.26; found: 369.2.
7.2.7. Siloxy alkyne 1g. 1H NMR (500 MHz, CDCl3) d 4.64
(s, 1H), 4.56 (s, 1H), 2.42 (m, 1H), 2.08 (dd, 1H, J¼8.5,
14.5 Hz), 1.58–1.48 (m, 2H), 1.42–1.32 (m, 2H), 1.24 (h,
3H, J¼7.5 Hz), 1.12 (d, 18H, J¼7.5 Hz), 1.07 (m, 2H),
0.87 (t, 3H, J¼7.0 Hz), 0.01 (s, 9H); 13C NMR (125 MHz,
CDCl3) d 145.6, 108.8, 88.0, 45.3, 38.0, 33.9, 28.7, 26.5,
20.5, 17.4, 14.0, 11.8, ꢀ1.3; IR (neat, cmꢀ1) 3073, 2955,
2869, 2274, 2078, 1632, 1464; MS (APCI) calculated for
[C22H45OSi2]+: 381.30; found: 381.2.
7.2.14. Siloxy alkyne 1n. 1H NMR (400 MHz, CDCl3)
d 2.25 (t, 2H, J¼2.4 Hz), 2.18–2.13 (m, 2H), 1.51–1.36
(m, 4H), 1.30–1.22 (m, 3H), 1.20 (s, 6H), 1.12 (d, 18H,
J¼7.1 Hz), 0.90 (t, 3H, J¼7.2 Hz); 13C NMR (100 MHz,
CDCl3) d 87.2, 81.9, 77.6, 37.8, 34.5, 31.2, 30.1, 29.2,
21.9, 18.5, 17.3, 13.6, 11.8; IR (neat, cmꢀ1) 2961, 2869,