Addition of Alcohol Pronucleophiles
J . Org. Chem., Vol. 66, No. 1, 2001 275
found: C 71.59, H 12.75; HRMS calcd for C17H36OSi: 284.2536,
found: 284.2535.
Ch olester yl eth er 3m : 1H NMR (300 MHz, CDCl3) δ 5.35
(m, 1H), 4.99 (s, 1H), 4.86 (s, 1H), 3.94 (s, 2H), 3.21-3.14 (m,
1H), 2.37-2.34 (m, 1H), 2.25-2.17 (m, 1H), 2.07-1.76 (m, 9H),
1.64-1.23 (m, 24H), 1.19-1.00 (m, 8H), 0.92-0.87 (m, 14H),
0.67 (s, 3H); 13C NMR (300 MHz, CDCl3) 147.0, 141.1, 121.5,
110.7, 78.4, 76.8, 56.8, 56.1, 50.2, 42.3, 39.8, 39.5, 39.1, 37.3,
36.9, 36.2, 35.8, 33.2, 31.9, 31.9, 29.5, 29.4, 29.3, 28.4, 28.2,
28.0, 27.6, 24.3, 23.8, 22.8, 22.7, 22.6, 21.1, 19.4, 18.7, 14.1,
11.9 ppm; HRMS calcd for C38H66O: 538.5114, found: 538.5121.
Bis(2-m et h ylen ed ecyl) et h er (3f): 1H NMR (300 MHz,
CDCl3) δ 4.99 (s, 2H), 4.89 (s, 2H), 3.88 (s, 4H), 2.04 (t, J )
7.15, 7.9 Hz, 4H), 1.44 (m, 4H), 1.27 (s, 20 H), 0.88 (t, J ) 6.4,
6.9 Hz, 6H); 13C NMR (300 MHz, CDCl3) 146.5, 111.0, 72.8,
33.2, 31.9, 29.5, 29.4, 29.3, 27.6, 22.7, 14.1 ppm; IR (neat) 3074,
2956, 2925, 2854, 1615, 1465, 1396, 1377, 1350, 1255, 1089,
1028, 900, 721, 665 cm-1. HRMS calcd for C22H42O: 322.3234,
found: 322.3220.
1
Glu cop yr a n osyl eth er 3n : H NMR (300 MHz, CDCl3) δ
2-(Allyloxym eth yl)d ec-1-en e (3g): 1H NMR (300 MHz,
CDCl3) δ 5.99-5.86 (m, 1H), 5.31-5.24 (dq, J ) 1.65, 17 Hz,
1H), 5.20-5.15 (dq, J ) 1.29, 10.4 Hz, 1H), 5.00 (d, J ) 0.73
Hz, 1H), 4.89 (d, J ) 0.74 Hz, 1H), 3.96 (dt, J ) 1.47, 5.7 Hz,
2H), 3.91 (s, 2H), 2.05 (t, J ) 7.51 Hz, 2H), 1.45 (t, J ) 7.3 Hz,
2H), 1.27 (s, 10H), 0.88 (t, J ) 6.4 Hz, 3H); 13C NMR (300 MHz,
CDCl3) 146.4, 134.9, 116.8, 111.1, 73.1, 70.9, 33.2, 31.9, 29.5,
29.4, 29.3, 27.6, 22.7, 14.1 ppm; IR (neat) 3080, 3014, 2956,
2925, 2854, 1649, 1465, 1379, 1348, 1087, 1020, 989, 920, 900,
665 cm-1. Anal. Calcd for C14H26O (%): calcd: C 80.00, H 12.37;
found: C 80.06, H 12.42; HRMS calcd for C14H26O: 210.1984,
found: 210.1957.
2-(Bu toxym eth yl)d ec-1-en e (3h ): 1H NMR (300 MHz,
CDCl3) δ 4.98 (s, 1H), 4.87 (s, 1H) 3.89 (s, 2H), 3.39 (t, J ) 6.4
Hz, 2H), 2.04 (t, J ) 7.3 Hz, 2H), 1.58 (m, 2H), 1.54 (m, 2H),
1.27 (s, 12H), 0.92 (t, 3H), 0.88 (t, 3H); 13C NMR (300 MHz,
CDCl3) 146.7, 110.8, 73.8, 69.9, 33.1, 31.9, 29.5, 29.4, 29.3, 27.6,
22.7, 19.4, 14.1, 13.9 ppm; IR (neat) 3074, 2958, 2927, 2856,
2734, 1652, 1465, 1379, 1350, 1299, 1267, 1234, 1099, 1053,
1014, 964, 933, 898, 723 cm-1. Anal. Calcd for C15H30O (%):
calcd: C 79.64, H 13.27; found: C 79.47, H 13.25; HRMS calcd
for C15H30O: 226.2297, found: 226.2308.
7.36-7.14 (m, 20H), 5.22 (ds, J ) 1.5 Hz, 1H), 5.02-4.90 (m,
3H), 4.84-4.71 (m, 3H), 4.65-4.51 (m, 3H), 4.47-4.37 (m, 2H),
4.03 (d, J ) 13.6 Hz, 1H), 3.77-3.44 (m, 6H), 2.04 (p, J ) 6.7,
7.0, 6.9 Hz, 1H), 1.41-1.23 (m, 12H), 0.86 (t, 6H); 13C NMR
(300 MHz, CDCl3) 147.8, 138.6, 138.3, 138.2, 138.1, 128.4,
128.3, 128.2, 128.0, 127.8, 127.7, 127.6, 127.5, 110.6, 102.8,
84.7, 82.3, 77.9, 75.7, 75.0, 74.9, 74.9, 73.4, 70.2, 68.9, 43.5,
33.8, 33.6, 29.6, 29.5, 22.9, 22.8, 14.1 ppm; IR (neat) 3087,
3060, 3030, 2956, 2925, 2858, 1730, 1647, 1604, 1496, 1454,
1398, 1361, 1328, 1261, 1207, 1155, 1089, 1072, 1063, 906, 802,
734, 696 cm-1; HRMS calcd for C46H58O6: 706.4243, found:
706.4236.
2-(Ben zyloxym eth yl)-5-p h en ylp en t-1-en e (3o): 1H NMR
(300 MHz, CDCl3) δ 7.32-7.16 (m, 10H), 5.07 (s, 1H), 4.95 (s,
1H), 4.81 (s, 2H), 3.96 (s, 2H), 2.62 (dt, J ) 2.4, 7.14 Hz, 2H),
2.14 (t, J ) 7.5, 7.15 Hz, 2H), 1.80 (dp, J ) 2.4, 7.4 Hz, 2H);
13C NMR (300 MHz, CDCl3) 145.8, 142.3, 138.4, 128.4, 128.4,
128.3, 127.7, 127.5, 125.7, 111.8, 73.1, 71.9, 35.6, 32.7, 29.3
ppm; IR (neat) 3062, 3026, 2935, 2856, 1651, 1602, 1496, 1452,
1203, 1097, 1074, 1028, 904, 736, 698 cm-1. Anal. Calcd for
C
19H22O (%): calcd: C 85.66, H 8.33; found: C 85.37, H 8.54;
2-(sec-Bu toxym eth yl)d ec-1-en e (3i): 1H NMR (300 MHz,
CDCl3) δ 5.0 (s, 1H), 4.85 (s, 1H), 3.96-3.83 (dd, J ) 12.5,
16.5 Hz, 2H), 3.34 (m, J ) 6.2, 6.0 Hz, 1H), 2.05 (t, J ) 7.3
Hz, 2H), 1.50 (m, 2H), 1.44 (dm, J ) 1.3, 6.2, 7.5 Hz, 2H), 1.27
HRMS calcd for C19H22O: 266.1671, found: 266.1670.
2-(Be n zyloxym e t h yl)-3-p h e n e t h yl-5-p h e n ylp e n t -1-
1
en e (3p ): H NMR (300 MHz, CDCl3) δ 7.35-7.11 (m, 15H),
(s, 10H), 1.13 (d, J ) 6.2 Hz, 3H), 0.90 (overlapping t, 6H); 13
C
5.29 (s, 1H), 5.04 (s, 1H), 4.54 (s, 2H), 3.99 (s, 2H), 2.56 (m, J
) 7.15, 8.1 Hz 4H), 2.19 (p, J ) 7.15, 6.97 Hz 1H), 1.76 (q, J
) 6.97, 8.1 Hz 4H); 13C NMR (300 MHz, CDCl3) 147.6, 142.5,
138.3, 128.4, 128.3, 127.6, 127.5, 125.6, 112.5, 72.4, 71.6, 43.1,
35.8, 33.6 ppm; IR (neat) 3084, 3062, 3026, 2929, 2856, 1645,
NMR (300 MHz, CDCl3) 147.2, 110.6, 76.0, 71.2, 33.2, 31.9,
29.5, 29.5, 29.3, 29.2, 27.7, 22.7, 19.1, 14.1, 9.9 ppm; IR (neat)
3074, 2962, 2927, 2856, 1654 (d), 1465, 1373, 1338, 1174, 1137,
1116, 1078, 1024, 966, 898, 723 cm-1. Anal. Calcd for C15H30
O
(%): calcd: C 79.64, H 13.27; found: C 79.85, H 13.15; HRMS
calcd for C15H30O: 226.2295, found: 226.2272.
1602, 1494, 1454, 1361, 1203, 1099, 1028, 906, 746, 698 cm-1
.
Anal. Calcd for C27H30O (%): calcd: C 87.51, H 8.17; found:
C 87.36, H 8.07; HRMS calcd for C27H30O: 370.2297, found:
370.2297.
2-(ter t-P en toxym eth yl)dec-1-en e (3j): 1H NMR (300 MHz,
CDCl3) δ 5.03 (s, 1H), 4.83 (s, 1H), 3.76 (s, 2H) 2.04 (t, J )
7.15 Hz, 2H), 1.51 (m, J ) 7.4 Hz, 2H), 1.27 (s, 12H), 1.16 (s,
6H), 0.88 (t, J ) 7.51, 6.6 Hz, 6H); 13C NMR (300 MHz, CDCl3)
147.8, 109.8, 74.9, 64.3, 33.4, 32.9, 31.9, 29.5, 29.3, 27.8, 25.0,
22.7, 14.1, 8.3 ppm; IR (CCl4) 3074, 2962, 2925, 2856, 1716,
1654, 1643, 1379, 1363, 1294, 1240, 1178, 1157, 1080, 896, 723
cm-1. Anal. Calcd for C16H32O (%): calcd: C 80.00, H 13.30;
found: C 80.10, H 12.45; HRMS calcd for C16H32O: 240.2453,
found: 240.2423.
12: 1H NMR (300 MHz, CDCl3) δ 7.20-6.82 (m, 4H), 4.79
(s, 1H), 4.71 (s, 1H), 4.48 (s, 2H), 2.75 (m, 2H), 2.28 (m, 2H),
1.76 (m, 2H); 13C NMR (300 MHz, CDCl3) 157.0, 147.2, 137.2,
130.0, 127.5, 124.4, 121.6, 116.2, 81.3, 34.3, 32.7, 31.3 ppm;
IR (neat) 3072, 3020, 2977, 2927, 2850, 1645, 1602, 1583, 1490,
1456, 1438, 1404, 1352 (d), 1288 (d), 1255, 1234, 1209, 1182,
1147, 1101, 1051, 1008, 997, 968, 935, 906, 819 cm-1. Anal.
Calcd for C12H14O (%): calcd: C 82.71, H 8.10; found: C 82.62,
H 8.21; HRMS calcd for C12H14O: 174.1045, found: 174.1049.
15: 1H NMR (300 MHz, CDCl3) δ 6.93 (t, J ) 7.69, 7.72 Hz,
1H), 6.68 (d, J ) 7.33 Hz, 1H), 6.59 (d, J ) 7.90 Hz, 1H), 4.81
(s, 1H), 4.71 (qs, 2H), 3.52 (s, 2H), 2.85 (m, 2H), 2.45 (t, J )
6.43, 6.22 Hz, 2H), 1.71 (m, 2H); 13C NMR (300 MHz, CDCl3)
151.9, 147.2, 144.4, 126.4, 121.8, 113.6, 111.1, 39.9, 35.0, 33.5,
28.3 ppm; HRMS calcd for C12H14O: 174.1045, found: 174.1059.
1
2-(Cycloh exyloxym eth yl)d ec-1-en e (3k ): H NMR (300
MHz, CDCl3) δ 5.09 (s, 1H), 4.83 (s, 1H), 3.89 (s, 2H), 3.29 (m,
1H), 1.99 (m, 2H), 1.73 (m, 2H), 1.53 (m, 1H), 1.37-1.17 (m,
18 H), 0.87 (t, J ) 6.6 Hz, 6H); 13C NMR (300 MHz, CDCl3)
149.6, 109.9, 76.9, 69.0, 43.4, 33.9, 32.2, 29.6, 25.9, 24.2, 22.9,
14.1 ppm; IR (neat) 3080, 2956, 2929, 2858, 1716, 1647, 1452,
1402, 1377, 1361, 1350, 1259, 1095, 1024, 954, 900, 804 cm-1
HRMS calcd for C18H34O: 266.2610, found: 266.2590.
;
2-(Cyclooctyloxym eth yl)d ec-1-en e (3l): 1H NMR (300
MHz, CDCl3) δ 4.98 (s,1H), 4.85 (s, 1H), 3.88 (s, 2 H), 3.51-
3.38 (m, 1H), 2.04 (t, J ) 7.15, 7.8 Hz, 2H),1.85-1.42 (m, 15H),
1.27 (s,br, 11H), 0.88 (t, J ) 6.4, 6.9 Hz, 3H); 13C NMR (300
MHz, CDCl3) 147.2, 110.5, 78.8, 70.9, 33.2, 31.9, 31.5, 29.5,
29.4, 29.3, 27.7, 27.3, 25.5, 23.2, 22.7, 14.1 ppm; IR (neat) 3072,
2923, 2854, 2694, 1651, 1467, 1446, 1377, 1355, 1257, 1118,
1078, 896 cm-1; HRMS calcd for C19H36O: 280.2766, found:
280.2758.
1
Su p p or tin g In for m a tion Ava ila ble: Copies of H NMR
spectra of 3a , 3b, 3c, 3c′, 3d , 3e, 3f, 3g, 3h , 3i, 3j, 3k , 3l, and
12, preparation of compounds 11 and 13, ORTEP and X-ray
data of 15. This material is available free of charge via the
Internet at http://pubs.acs.org.
J O001428J