Y. Naruse et al. / Tetrahedron 66 (2010) 7035e7040
7039
3402 (br), 2800e2950, 1685, 1466, 1409, 1377, 1329, 827, 604 cmꢀ1
Anal. Calcd (%) for C11H24GeO (244.95): C 53.94, H 9.88; found: C
54.11, H 9.82.
.
(H,H)¼11.2 Hz, 1H), 5.28 (d, 3J (H,H)¼17.6 Hz, 1H), 5.66 (dd, 3J (H,
H)¼11.2, 17.6 Hz, 1H); 13C NMR (C6D6)
d
ꢀ2.9, 14.1, 22.7, 22.9, 32.1,
33.4, 88.7, 111.8, 115.5 (q, 3J (H,H)¼286.3 Hz), 137.6, 156.6 (q, 3J (H,
H)¼41.0 Hz). MS (EI) 73 (100), 199 (13). IR: 2880e3020, 1778, 1632,
1378, 1253, 1219, 1170, 841 cmꢀ1. Anal. Calcd (%) for C13H23F3O2Si
(298.14): C 52.68, H 7.74; found: C 52.90, H 7.74.
4.5. 3-(3-Acetoxyoct-1-enyl)trimethylsilane 1d, general
procedure
To a stirred solution of 5a (1.3 g, 6.8 mmol) in ether (52 mL) was
added vinylmagnesium bromide (1.0 M in THF, 9.4 mL, 9.4 mmol)
dropwise at ꢀ75 ꢁC, followed by acetyl chloride (1.0 mL, 15 mmol).
The reaction mixture was stirred overnight, gradually being
warmed to rt. It was poured into satd NH4Cl aq, and extracted with
ether several times. The combined extracts were dried over NaSO4,
concentrated in vacuo and purified by SGC gave a colorless oil
4.9. 3-(3-Acetoxyoct-1-enyl)trimethylgermane 1k
Yield: 38%. 1H NMR (CDCl3)
d
0.17 (s, 9H), 0.85 (t, 3J (H,H)¼7.6 Hz,
3H), 1.20e1.30 (m, 6H), 1.57e1.61 (m, 1H), 2.05 (s, 3H), 2.06e2.12
(m, 1H), 4.95 (d, 3J (H,H)¼10.8 Hz, 1H), 4.95 (d, 3J (H,H)¼17.6 Hz,
1H), 5.68 (dd, 3J (H,H)¼10.8, 17.6 Hz, 1H); (C6D6)
d 0.54 (s, 9H), 1.08
(t, 3J (H,H)¼7.2 Hz, 3H), 1.37e1.67 (m, 6H), 1.84 (m, 1H), 1.91 (s, 3H),
2.50 (m, 1H), 5.18 (dd, 3J (H,H)¼1.6, 11.2 Hz, 1H), 5.32 (dd, 3J (H,H)¼
1.6, 17.2 Hz, 1H), 5.89 (dd, 3J (H,H)¼11.2, 17.6 Hz, 1H); 13C NMR
(0.62 g, 38%). 1H NMR (CDCl3)
d
0.00 (s, 9H), 0.81 (t, 3J (H,H)¼6.8 Hz,
3H), 1.20e1.30 (m, 6H), 1.53e1.60 (m, 1H), 1.99 (s, 3H), 2.06e2.12
(m, 1H), 4.92 (dd, 3J (H,H)¼1.6, 18.8 Hz, 1H), 4.93 (dd, 3J (H,H)¼1.6,
(C6D6)
d
ꢀ1.6, 14.2, 20.6, 23.0, 23.6, 32.4, 35.1, 82.8, 109.5, 140.6,
10.8 Hz, 1H), 5.68 (dd, 3J (H,H)¼10.8, 18.8 Hz, 1H); (C6D6)
d 0.23 (s,
169.8. MS (EI) 115 (59), 117 (85), 118 (25), 119 (100), 121 (32). IR:
2880e2950, 1734, 1628, 1368, 1261, 820, 592 cmꢀ1. Anal. Calcd (%)
for C13H22O2Si (286.98): C 54.41, H 9.13; found: C 54.63, H 9.25.
9H), 1.08 (t, 3J (H,H)¼7.6 Hz, 3H), 1.37e1.63 (m, 6H), 1.82 (td-like m,
1H), 1.91 (s, 3H), 2.51 (td-like m, 1H), 5.25 (dd, 3J (H,H)¼1.5, 14.6 Hz,
1H), 5.32 (dd, 3J (H,H)¼1.5, 17.1 Hz, 1H), 5.89 (dd, 3J (H,H)¼14.6,
17.1 Hz, 1H); 13C NMR (CDCl3)
d
ꢀ1.9, 14.2, 20.6, 23.0, 23.4, 32.5,
4.10. 3-(3-(Dichloroacetoxy)oct-1-enyl)trimethylgermane 1l
34.2, 81.6, 110.3, 140.5, 169.9. MS (EI) 73 (100). IR: 2880e2950, 1733,
1628, 1368, 1265, 840, 755, 628 cmꢀ1. Anal. Calcd (%) for C13H22O2Si
(286.98): C 64.41, H 10.81; found: C 64.22, H 10.83.
Ethylmagnesium chloride was used instead of vinylmagnesium
bromide. Yield: 48%. 1H NMR (CDCl3)
d
0.22 (s, 9H), 0.85 (t, 3J (H,H)¼
7.2 Hz, 3H), 1.22e1.30 (m, 6H), 1.65e1.72 (m, 1H), 2.14e2.21 (m, 1H),
5.01 (dd, 3J (H,H)¼0.8, 10.8 Hz, 1H), 4.95 (dd, 3J (H,H)¼0.8, 17.6 Hz,
4.6. 3-(3-(Chloroacetoxy)oct-1-enyl)trimethylsilane 1e
1H), 5.68 (dd, 3J (H,H)¼10.8, 17.6 Hz, 1H); (C6D6)
d 0.47 (s, 9H), 1.07
Ethylmagnesium chloride was used instead of vinylmagnesium
(t, 3J (H,H)¼7.2 Hz, 3H), 1.34e1.48 (m, 4H), 1.54e1.63 (m, 2H), 1.79
(m, 1H), 2.45 (m, 1H), 5.15 (dd, 3J (H,H)¼1.6, 11.2 Hz, 1H), 5.35 (dd, 3J
(H,H)¼1.6, 17.2 Hz, 1H), 5.80 (dd, 3J (H,H)¼11.2, 17.6 Hz, 1H); 13C
bromide. Yield: 24%. 1H NMR (CDCl3)
d
0.07 (s, 9H), 0.86 (t, 3J (H,H)¼
6.8 Hz, 3H), 1.25 (m, 6H), 1.60 (m, 1H), 2.16 (m, 1H), 4.05 (s, 2H), 5.01
(dd, 3J (H,H)¼1.6, 12.4 Hz, 1H), 5.05 (dd, 3J (H,H)¼1.6, 16.8 Hz, 1H),
NMR (C6D6)
d
ꢀ2.1,14.2, 22.9, 23.3, 32.2, 34.6, 65.3, 87.1,110.4,139.0,
5.74 (dd, 3J (H,H)¼16.8, 12.4 Hz, 1H); (C6D6)
d
0.34 (s, 9H), 1.08 (t, 3J
163.4. MS (EI) 115 (56), 117 (76), 118 (24), 119 (100), 121 (22). IR:
(H,H)¼6.8 Hz, 3H), 1.33e1.63 (m, 6H), 1.77 (m, 1H), 2.47 (m, 1H),
3.66 (s, 2H), 5.19 (dd, 3J (H,H)¼1.6, 11.2 Hz, 1H), 5.32 (dd, 3J (H,H)¼
1.6, 17.2 Hz, 1H), 5.81 (dd, 3J (H,H)¼11.2, 17.2 Hz, 1H); 13C NMR
2880e2950, 1734, 1629, 1466, 1411, 1307, 1196, 906, 826, 596 cmꢀ1
.
4.11. Thermal rearrangement of the allyl esters, general
procedure: 3-(1-acetoxyoct-2-enyl)trimethylsilane 2d
(C6D6)
d
ꢀ2.1, 14.2, 22.9, 23.2, 32.4, 33.9, 40.9, 84.2, 111.0, 139.6,
166.2. MS (EI) 73 (100), 199 (19). IR: 2880e2950, 1733, 1466, 1411,
1316, 1250, 841 cmꢀ1. Anal. Calcd (%) for C13H25ClO2Si (276.87): C
56.39, H 9.10, Cl 12.80; found C 56.64, H 9.09, Cl 12.69.
A benzene-d6 solution of 1d (19 mg, 0.080 mmol) and naph-
thalene as the internal standard (4.2 mg) was sealed in an NMR
tube, and heated with a Kugel Rohr apparatus monitoring the
temperature with a thermometer. Completion of the reaction was
determined by measuring by 1H NMR (48 h). The yield (48%) and
the diastereoselectivity (Z/E¼58:42) were determined by 1H NMR.
4.7. 3-(3-(Dichloroacetoxy)oct-1-enyl)trimethylsilane 1g
Ethylmagnesium chloride was used instead of vinylmagnesium
bromide. Yield: 31%. 1H NMR (CDCl3)
d
0.10 (s, 9H), 0.85 (t, 3J (H,H)¼
1H NMR (C6D6)
d 0.29 (s, 9H for E-isomer), 0.36 (s, 9H for Z-isomer),
6.8 Hz, 3H), 1.20e1.36 (m, 6H), 1.65e1.71 (m, 2H), 2.16e2.23 (m,
1H), 5.07 (dd, 3J (H,H)¼11.2, 0.9 Hz, 1H), 5.05 (dd, 3J (H,H)¼17.2,
0.9 Hz, 1H), 5.74 (dd, 3J (H,H)¼17.2, 11.2 Hz, 1H), 5.92 (s, 1H); (C6D6)
1.08 and 1.09 (overlapping two t’s, 3J (H,H)¼7.0 Hz, 3H), 1.36e1.60
(m, 6H), 1.89 (s, 3H for E-isomer), 1.90 (s, 3H for Z-isomer), 2.28 (t, 3J
(H,H)¼7.6 Hz, 2H for Z-isomer), 2.34 (t, 3J (H,H)¼7.6 Hz, 2H for E-
isomer), 4.95 (d, 3J (H,H)¼6.4 Hz, 2H for Z-isomer), 4.98 (d, 3J (H,
H)¼6.0 Hz, 2H for E-isomer), 6.21 (t, 3J (H,H)¼6.0 Hz, 1H for E-iso-
mer), 6.38 (t, 3J (H,H)¼6.4 Hz, 1H for Z-isomer). MS (EI) 73 (100), 75
(43), 117 (51), 149 (13), 199 (7), 214 (5), 239 (6), 242 (4). IR:
2880e2960, 1744, 1248, 1376, 1229, 1026, 838 cmꢀ1. Anal. Calcd (%)
for C13H22O2Si (242.43): C 64.41, H 10.81%; found: C 64.17, H 10.57.
d
0.32 (s, 9H),1.07 (t, 3J (H,H)¼6.8 Hz, 3H),1.38 (m, 2H),1.45 (m, 2H),
1.53e1.62 (m, 2H), 1.77 (m, 1H), 2.48 (m, 2H), 5.18 (dd, 3J (H,H)¼1.6,
11.2 Hz, 1H), 5.37 (dd, 3J (H,H)¼1.6, 17.6 Hz, 1H), 5.61 (s, 1H), 5.76
(dd, 3J (H,H)¼11.2, 17.6 Hz, 1H); 13C NMR (C6D6)
d
ꢀ2.4, 14.2, 22.9,
23.1, 32.2, 33.7, 65.4, 85.2, 111.4, 138.8, 183.4. MS (EI) 73 (100), 185
(14), 189 (2), 199 (29), 311 (1). IR: 2880e2950, 1741, 1251, 839 cmꢀ1
.
Anal. Calcd (%) for C13H24Cl2O2Si (311.32): C 50.15, H 7.77, Cl 22.78;
found C 50.28, H 7.59, Cl 22.75.
4.12. 3-(1-Chloroacetoxyoct-2-enyl)trimethylsilane 2e
4.8. 3-(3-(Trifluoroacetoxy)oct-1-enyl)trimethylsilane 1h
A mixture of E- and Z-isomers. 1H NMR (C6D6)
d 0.27 (s, 9H for E-
Ethylmagnesium chloride was used instead of vinylmagnesium
isomer), 0.32 (s, 9H for Z-isomer), 1.08 and 1.09 (overlapping two
t’s, 3J (H,H)¼7.0 Hz, 3H), 1.36e1.60 (m, 6H), 2.24 (t, 3J (H,H)¼7.7 Hz,
2H for Z-isomer), 2.29 (t, 3J (H,H)¼7.7 Hz, 2H for E-isomer), 3.63 (s,
2H for E-isomer), 3.63 (s, 2H for Z-isomer), 4.87 (d, 3J (H,H)¼6.2 Hz,
2H for Z-isomer), 4.88 (d, 3J (H,H)¼7.0 Hz, 2H for E-isomer), 6.09 (t,
3J (H,H)¼7.0 Hz, 1H for E-isomer), 6.26 (t, 3J (H,H)¼6.2 Hz, 1H for Z-
isomer). IR: 2883e2953, 1741, 1249, 1169, 838 cmꢀ1. Anal. Calcd (%)
bromide, and trifluoroacetic anhydride was used as an acylating
agent. Yield: 86%. 1H NMR (CDCl3)
d
0.07 (s, 9H), 0.85 (t, 3J (H,H)¼
7.6 Hz, 3H), 1.20e1.36 (m, 6H), 1.71 (m, 1H), 2.25 (m, 1H), 5.06 (dd, 3J
(H,H)¼1.2, 16.8 Hz, 1H), 5.09 (dd, 3J (H,H)¼1.2, 11.2 Hz, 1H), 5.74 (dd,
3J (H,H)¼11.2, 16.8 Hz, 1H), (C6D6)
d
0.23 (s, 9H), 1.03 (t, 3J (H,H)¼
7.6 Hz, 3H), 1.26e1.59 (m, 6H), 1.75 (m, 1H), 2.47 (m, 1H), 5.12 (d, 3J