1338
Vol. 60, No. 10
1
Triisopropylsiloxymethyl Pivalate (14): Pale yellow oil. Pale yellow oil. H-NMR (CDCl ) δ: 1.06–1.17 (21H, m),
3
1
H-NMR (CDCl ) δ: 1.02–1.20 (21H, m), 1.21 (9H, s), 5.40 (s, 1.21–1.38 (20H, m), 1.51–1.70 (4H, m), 2.17 (3H, s), 2.32 (2H,
3
13
13
2
H); C-NMR (CDCl ) δ: 11.8, 17.6, 27.0, 38.7, 84.4, 177.7. t, J=7.6Hz), 4.05 (2H, t, J=6.8Hz), 5.46 (2H, s). C-NMR
3
1
−
IR (neat) cm : 2945, 2868, 1747, 1463, 1099, 1030, 951, 882, (CDCl ) δ: 11.8, 17.7, 20.9, 24.7, 25.9, 28.6, 29.1, 29.2, 29.4,
7
3
−1
50, 684. ESI-MS m/z: 311.2038 (Calcd for C H NaO Si: 29.4, 29.5, 29.6, 34.4, 64.6, 83.9, 172.9. IR (neat) cm : 2925,
15 32 3
3
11.2018).
2855, 1742, 1463, 1364, 1219, 772, 547, 419. FAB-MS m/z: 487
+
Triisopropylsiloxymethyl 1-Adamantanecarboxyate (15): [(M+1) ], 457. FAB-MS m/z: 487.3839 (Calcd for C H O Si:
2
7
55
5
1
Pale yellow oil. H-NMR (CDCl ) δ: 1.04–1.18 (21H, m), 1.71 487.3819)
3
(
6H, t, J=14.9Hz), 1.90 (6H, s), 2.02 (3H, s), 5.45 (2H, s).
Triisopropylsiloxymethyl 15-Methoxypentadecanoate (19g):
13
1
C-NMR (CDCl ) δ: 11.8, 17.6, 27.9, 36.5, 38.7, 40.6, 84.3, Colorless oil: H-NMR (CDCl ) δ: 1.01–1.19 (21H, m),
3
3
−1
1
4
3
76.9. IR (neat) cm : 2907, 2865, 1730, 1455, 1163, 1044, 472, 1.21–1.38 (20H, m), 1.50–1.68 (4H, m), 2.32 (2H, t, J=7.3Hz),
13
35, 419, 404; ESI-MS m/z: 389.2492 (Calcd for C H NaO Si: 3.36 (2H, t, J=6.8Hz), 5.46 (2H, s). C-NMR (CDCl ) δ: 11.9,
21
38
3
3
89.2487).
17.7, 24.7, 26.1, 29.0, 29.2, 29.4, 29.5, 29.6, 29.6, 29.6, 34.5,
−1
Triisopropylsiloxymethyl Methyl Nonanedioate (17): Pale 58.5, 72.9, 83.9, 173.0. IR (neat) cm : 2926, 2858, 1748, 1461,
1
yellow oil. H-NMR (CDCl ) δ: 0.97–1.08 (21H, m), 1.61 (4H, 1117, 963, 762, 551, 458, 404. ESI-MS m/z: 481.3681 (Calcd for
3
m), 2.31 (4H, dt, J=7.6, 7.6Hz), 3.66 (3H, s), 5.46 (2H, s). C H NaO Si: 481.3689).
2
6
54
4
13
C-NMR (CDCl ) δ: 11.8, 17.6, 24.7, 28.8, 33.9, 34.3, 51.3,
Triisopropylsiloxymethyl
15-(Benzyloxy)pentadecanoate
3
−1
1
8
3.8, 172.8, 174.1. IR (neat) cm : 2938, 1741, 1513, 1168, 970, (19i): Colorless oil: H-NMR (CDCl ) δ: 1.06–1.16 (21H, m),
3
8
11, 733, 546. ESI-MS m/z: 411.2559 (Calcd for C H NaO Si: 1.21–1.40 (20H, m), 1.58–1.64 (4H, m), 2.32 (2H, t, J=7.6Hz),
20 40 5
411.2547).
3.46 (2H, t, J=6.8Hz), 4.50 (2H, s), 5.46 (2H, s), 7.26–7.34
13
Triisopropylsiloxymethyl 15-tert-Butyldimethylsiloxypenta- (5H, m). C-NMR (CDCl ) δ: 11.9, 17.7, 24.7, 26.2, 29.4, 29.5,
3
1
decanoate (19b): Pale yellow oil. H-NMR (CDCl ) δ: 0.01 29.6, 29.6, 29.6, 29.8, 34.4, 70.5, 72.8, 83.9, 127.4, 127.6, 128.3,
3
−1
(6H, s), 0.84 (9H, s), 0.98–1.15 (21H, m), 1.15–1.41 (20H, 138.7, 172.9. IR (neat) cm : 2925, 2857, 1745, 1460, 1361,
m), 1.45 (2H, quin, J=6.8Hz), 1.57 (2H, quin, J=6.8Hz), 1101, 952, 882, 736, 687, 496. ESI-MS m/z: 557.4000 (Calcd
2
.37 (2H, t, J=7.3Hz), 3.54 (2H, t, J=6.9Hz), 5.41 (2H, s). for C H NaO Si: 557.4002).
32 58 4
13
C-NMR (CDCl ) δ: −5.2, 11.9, 17.7, 18.4, 24.7, 25.8, 26.0,
Triisopropylsiloxymethyl 15-(4-Methoxybenzyloxy)penta-
3
1
29.1, 29.3, 29.4, 29.5, 29.6, 29.6, 32.9, 34.5, 63.3, 84.0, 172.4. decanoate (19j): Colorless oil: H-NMR (CDCl ) δ: 1.05–1.19
3
−1
IR (neat) cm : 2930, 2859, 1748, 1463, 1377, 1251, 1157, 1102, (21H, m), 1.22–1.38 (20H, m), 1.55–1.66 (4H, sep, J=7.3Hz),
59, 881, 838, 772, 683. ESI-MS m/z: 581.4398 (Calcd for 2.32 (2H, t, J=7.3Hz), 3.43 (2H, t, J=6.8Hz), 3.80 (3H, s),
C H NaO Si : 581.4397). 4.43 (2H, s), 5.46 (2H, s), 6.87 (2H, d, J=8.6Hz), 7.26 (2H,
9
3
1
66
4
2
13
Triisopropylsiloxymethyl
15-Triisopropylsiloxypentade- d, J=8.6Hz). C-NMR (CDCl ) δ: 11.9, 17.7, 24.7, 26.2, 29.1,
3
1
canoate (19c): Pale yellow oil. H-NMR (CDCl ) δ: 1.02–1.20 29.2, 29.4, 29.4, 29.5, 29.6, 29.7, 34.5, 55.2, 70.2, 72.4, 83.9,
3
−1
(42H, m), 1.21–1.39 (20H, m), 1.49–1.69 (4H, m), 2.31 (2H, 113.7, 129.1, 130.8, 159.1, 173.0. IR (neat) cm : 2927, 2857,
13
t, J=7.6Hz), 3.66 (2H, t, J=6.8Hz), 5.46 (2H, s). C-NMR 1744, 1460, 1098, 772, 678, 493, 450. ESI-MS m/z: 587.4089
(CDCl ) δ: 11.9, 12.0, 17.7, 18.0, 24.7, 25.8, 29.2, 29.4, 29.5, (Calcd for C H NaO Si: 587.4107).
3
33 60
5
−1
29.6, 29.6, 33.0, 34.4, 63.5, 83.9, 173.4. IR (neat) cm : 2938,
Triisopropylsiloxymethyl
(2S)-2-[(tert-Butoxycarbonyl)-
2
8
2862, 1749, 1463, 1383, 1101, 992, 882, 772, 682, 425. ESI-MS amino]-3-methylbutanoate (20): Colorless oil: [α]
−3.67
(c=1.01, CHCl ). H-NMR (CDCl ) δ: 0.90 (3H, d, J=6.8Hz),
D
1
m/z: 623.4872 (Calcd for C H NaO Si : 623.4866).
3
4
72
4
2
3
3
Triisopropylsiloxymethyl 15-tert-Butyldiphenylsiloxypenta- 0.98 (3H, d, J=6.8Hz) 1.05–1.18 (21H, m), 1.56 (9H, s),
1
decanoate (19d): Pale yellow oil. H-NMR (CDCl ) δ: 2.15–2.25 (1H, m), 4.25 (1H, dd, J=9.5, 4.0Hz), 4.63 (1H,
3
1
.05–1.20 (30H, m), 1.21–1.38 (20H, m), 1.56 (2H, quin, d, J=9.0Hz), 5.46 (1H, d, J=3.6Hz), 5.58 (1H, d, J=3.7Hz);
J=5.1Hz), 1.62 (2H, quin, J=7.6Hz), 2.32 (2H, t, J=7.5Hz),
.64 (2H, t, J=6.3Hz), 5.46 (2H, s,), 7.35–7.44 (6H, m), 7.66 79.6, 84.6, 155.6, 171.6. IR (neat) cm : 3380, 2955, 2871, 1718,
4H, dd, J=5.4, 1.6Hz). C-NMR (CDCl ) δ: 11.9, 17.8, 19.2, 1505, 1472, 1362, 1224, 1167, 976, 881, 771, 684. ESI-MS m/z:
4.0, 25.8, 26.9, 29.1, 29.3, 29.4, 29.5, 29.6, 29.6, 29.6, 32.6, 426.2648 (Calcd for C H NNaO Si: 426.2651).
4.5, 64.0, 84.0, 127.5, 129.4, 134.2, 135.7, 173.0. IR (neat)
cm : 2926, 2857, 1748, 1464, 1464, 1218, 1105, 882, 771, 701, amino}-4-methylpentanoate (21): Colorless oil: [α] −10.7
12, 425. ESI-MS m/z: 705.4752 (Calcd for C H NaO Si : (c=1.01, CHCl ). H-NMR (CDCl ) δ: 0.96 (6H, t, J=5.6Hz),
1.00–1.19 (21H, m), 1.65–1.78 (2H, m), 4.35–4.42 (1H, m),
15-(Tetrahydro-2H-pyran-2-yl- 5.08–5.15 (3H, m), 5.48 (1H, d, J=4.1Hz), 5.53 (1H, d,
oxy)pentadecanoate (19e): Pale yellow oil. H-NMR (CDCl ) J=3.6Hz), 7.27–7.38 (5H, m). C-NMR (CDCl ) δ: 11.8, 17.6,
δ: 1.05–1.19 (21H, m), 1.21–1.41 (20H, m), 1.48–1.86 (10H, 21.8, 22.8, 24.7, 41.7, 52.6, 66.9, 84.7, 128.0, 128.1, 128.4,
m), 2.32 (2H, t, J=7.6Hz), 3.38 (1H, dt, J=6.8, 6.6Hz), 3.50 136.3, 155.8, 172.2. IR (neat) cm : 2946, 2867, 1727, 1523,
1H, sex, J=3.7Hz), 3.73 (1H, dt, J=7.1, 6.8Hz), 3.87 (1H, 1465, 1113, 1050, 882, 693. FAB-MS m/z: 452 [(M+1) ].
ddt, J=7.3, 3.6, 3.6Hz), 4.57 (1H, t, J=2.7Hz), 5.46 (2H, s). FAB-MS m/z: 452.2831 (Calcd for C H NO Si: 452.2832).
C-NMR (CDCl ) δ: 11.9, 17.7, 19.7, 24.7, 25.5, 26.2, 29.1,
9.3, 29.4, 29.5, 29.6, 29.6, 29.7, 30.8, 34.5, 62.3, 67.7, 83.9, carbonyl]-2-pyrrolidinecarboxylate (22): Colorless oil: [α]
8.8, 173.0. IR (neat) cm : 2926, 2858, 1747, 1462, 1358, −49.5 (c=0.87, CHCl ). H-NMR (CDCl ) δ: 1.02–1.21 (21H,
103, 1029, 881, 771, 684. ESI-MS m/z: 551.4109 (Calcd for m), 1.88–2.18 (3H, m), 2.20–2.30 (1H, m), 3.50–3.56 (1H,
C H NaO Si : 551.4107). m), 3.60–3.70 (1H, m), 4.18 (0.5H, t, J=6.8Hz), 4.26 (0.5H, t,
Triisopropylsiloxymethyl 15-Acetoxypentadecanoate (19f): J=7.1Hz), 4.31–4.36 (1H, m), 4.38–4.48 (1H, m), 5.36 (0.5H, d,
13
C-NMR (CDCl ) δ: 11.8, 17.2, 17.6, 19.1, 28.3, 31.1, 58.4,
3
−1
3
(
13
3
2
3
2
0
41
5
Triisopropylsiloxymethyl
(2S)-2-{[(Benzyloxy)carbonyl]-
−1
28
D
1
5
41
70
4
2
3
3
705.4710).
Triisopropylsiloxymethyl
1
13
3
3
−1
+
(
2
4
42
5
1
3
Triisopropylsiloxymethyl (2S)-1-[(9H-Fluoren-9-ylmethoxy)-
3
2
8
2
9
D
−1
1
3
3
1
3
0
60
5
2