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Helvetica Chimica Acta – Vol. 94 (2011)
3 H). 13C-NMR (75 MHz, CDCl3): 177.4; 86.7; 86.1; 62.8; 62.5; 38.7; 38.3; 34.6; 28.6; 23.5; 22.0; 14.4. ESI-
MS: 251 ([M þ Na]þ). HR-MS: 251.1263 ([M þ Na]þ, C12H20NaO4þ ; calc. 251.1259).
(5R)-5-{[(tert-Butyl)dimethylsilyl]oxy}-16-[(4-methoxybenzyl)oxy]hexadec-6-yn-8-ol (14). As de-
scribed for 13, from 5 (0.60 g, 3.54 mmol) and 7 [20] (0.59 g, 2.12 mmol): 14 (0.09 g, 70%). Yellow liquid.
[a]2D5 ¼ þ43 (c ¼ 1.9, CHCl3). IR (KBr): 3411, 2945, 2931, 2857, 2010, 1611, 1513, 1463, 1360, 1249, 1087,
1
837, 778. H-NMR (300 MHz, CDCl3): 7.17 (d, J(A,B) ¼ 8.3, 2 H); 6.79 (d, J(A’,B’) ¼ 8.6, 2 H); 4.38 (s,
2 H); 4.34 – 4.28 (m, 2 H); 3.78 (s, 3 H); 3.38 (t, J ¼ 6.7, 2 H); 1.63 – 1.51 (m, 8 H); 1.43 – 1.25 (m, 12 H);
0.93 – 0.89 (m, 12 H); 0.08 (d, J ¼ 7.1, 6 H ) . 13C-NMR (75 MHz, CDCl3): 159.3; 130.7; 129.1; 113.7; 86.7;
84.9; 72.4; 62.8; 62.4; 55.0; 38.3; 37.8; 29.6; 29.4; 29.3; 29.2; 26.1; 25.8; 25.1; 22.3; 18.2; 14.1; ꢀ 4.4; ꢀ 4.9.
ESI-MS: 527 ([M þ Na]þ).
(5R)-5-{[(tert-Butyl)dimethylsilyl]oxy}-16-[(4-methoxybenzyl)oxy]hexadec-6-yn-8-one (4). As de-
scribed for 3, from 14 (0.5 g, 0.99 mmol): 4 (0.38 g, 77%). Colorless liquid. [a]2D5 ¼ þ41.80 (c ¼ 2.2,
CHCl3). IR (KBr): 2930, 2857, 2210, 1714, 1679, 1463, 1254, 1089, 838, 778. 1H-NMR (300 MHz, CDCl3):
7.2 (d, J(A,B) ¼ 8.3, 2 H); 6.82 (d, J(A’,B’) ¼ 8.3, 2 H); 4.45 (t, J ¼ 6.4, 1 H); 4.37 (s, 2 H); 3.78 (s, 3 H);
3.37 (t, J ¼ 6.4, 2 H); 2.49 (t, J ¼ 7.1, 2 H); 1.73 – 1.51 (m, 6 H); 1.42 – 1.25 (m, 12 H); 0.94 – 0.90 (m, 12 H);
0.13 (d, J ¼ 10.0, 6 H). 13C-NMR (75 MHz, CDCl3): 187.0; 159.0; 131.5; 129.1; 113.6; 96.1; 83.1; 72.4; 69.9;
62.7; 55.0; 45.3; 37.6; 29.7; 29.3; 29.2; 27.2; 26.2; 25.7; 23.9; 22.2; 18.2; 14.1; ꢀ 4.4; ꢀ 4.9. ESI-MS: 525
([M þ Na]þ). HR-MS: 525.3378 ([M þ Na]þ, C30H50NaO4Siþ; calc. 525.3376).
(5R,8S)-5-{[(tert-Butyl)dimethylsilyl]oxy}-16-[(4-methoxybenzyl)oxy]hexadec-6-yn-8-ol (14a). As
i
described for 13a, from 4 (0.30 g, 0.60 mmol): 14a (0.28 g, 91%). HPLC (Chiral Pak-IC, 3% PrOH/
hexane, flow rate 1 ml/min, 210 nm): tR (major) 8.488, tR (minor) 7.978; de 90%. Colorless liquid. [a]D25
¼
þ25.0 (c ¼ 1.85, CHCl3. IR (KBr): 3409, 2927, 2849, 2191, 1605, 1461, 1349, 1245, 1082, 835, 771. 1H-NMR
(300 MHz, CDCl3): 7.17 (d, J(A,B) ¼ 8.3, 2 H); 6.80 (d, J(A’,B’) ¼ 8.3, 2 H); 4.38 (s, 2 H); 4.32 (t, J ¼ 5.2,
2 H); 3.78 (s, 3 H); 3.37 (t, J ¼ 6.0, 2 H); 1.66 – 1.52 (m, 8 H); 1.43 – 1.29 (m, 12 H); 0.93 – 0.83 (m, 12 H);
0.09 (d, J ¼ 7.5, 6 H). 13C-NMR (75 MHz, CDCl3): 159.1; 130.7; 129.1; 113.7; 86.6; 85.1; 72.4; 62.8; 62.3;
55.0; 38.4; 37.8; 29.7; 29.5; 29.4; 29.2; 27.2; 25.9; 25.1; 22.3; 18.2; 14.1; ꢀ 4.5; ꢀ 5.0. ESI-MS: 527 ([M þ
Na]þ). HR-MS: 527.3555 ([M þ Na]þ, C30H52NaO4Siþ; calc. 527.3532).
1,1-{{(1R,4S)-1-Butyl-4-{[8-[(4-methoxybenzyl)oxy]octyl}but-2-yne-1,4-diyl}bis(oxy)}bis[(tert-bu-
tyl)dimethylsilane] (16). As described for 15, from 14a ((0.25 g, 0.49 mmol): 16 (0.25 g, 81%). Colorless
liquid. [a]2D5 ¼ þ27.5 (c ¼ 1.20, CHCl3). IR (KBr): 2905, 2829, 2195, 1603, 1505, 1454, 1245, 1075, 820, 767.
1H-NMR (300 MHz, CDCl3): 7.17 (d, J(A,B) ¼ 8.3, 2 H); 6.8 (d, J(A’,B’) ¼ 8.6, 2 H); 4.38 (s, 2 H); 4.31 (t,
J ¼ 6.4, 2 H); 3.78 (s, 3 H); 3.38 (t, J ¼ 6.4, 2 H); 1.62 – 1.52 (m, 8 H); 1.39 – 1.29 (m, 12 H); 0.93 – 0.89 (m,
21 H); 0.08 (d, J ¼ 7.1, 12 H). 13C-NMR (75 MHz, CDCl3): 159.3; 130.8; 129.3; 113.7; 85.5; 83.8; 72.5;
62.9; 55.2; 38.7; 38.4; 29.8; 29.6; 29.4; 29.2; 26.2; 27.4; 25.8; 25.2; 22.4; 18.2; 14.1; ꢀ 4.3; ꢀ 4.9. ESI-MS:
641 ([M þ Na]þ). HR-MS: 641.4367 ([M þ Na]þ, C36H66NaO4Siþ2 ; calc. 641.4397).
(9S,12R)-9,12-Bis{[(tert-butyl)dimethylsilyl]oxy}hexadec-10-yn-1-ol (18). As described for 17, from
16 (0.22 g, 0.36 mmol): 18 (0.12 g, 69%). Colorless liquid. [a]2D5 ¼ þ41.8 (c ¼ 0.7, CHCl3). IR (KBr): 3449,
2931, 2857, 2010, 1609, 1572, 1464, 1358, 1252, 1086. 1H-NMR (300 MHz, CDCl3): 4.43 (t, J ¼ 6.0, 2 H);
3.72 (t, J ¼ 6.7, 2 H); 1.74 – 1.61 (m, 8 H); 1.51 – 1.37 (m, 12 H); 1.04 – 1.0 (m, 21 H); 0.2 (m, 12 H).
13C-NMR (75 MHz, CDCl3): 85.5; 63.0; 38.7; 38.4; 32.8; 29.5; 29.2; 27.4; 25.8; 25.2; 22.4; 18.2; ꢀ 4.3;
ꢀ 4.9. ESI-MS: 521 ([M þ Na]þ). HR-MS: 521.3820 ([M þ Na]þ, C28H58NaO3Siþ2 ; calc. 521.3822).
(9S,12R)-9,12-Bis{[(tert-Butyl)dimethylsilyl]oxy}hexadec-10-ynoic Acid (20). As described for 19,
from 18 (0.10 g, 0.21 mmol): 20 (0.07 g, 86%). Colorless liquid. [a]2D5 ¼ þ26.2 (c ¼ 1.85, CHCl3). IR
(KBr): 3411, 2931, 2857, 2015, 1678, 1513, 1463, 1249, 1087. 1H-NMR (300 MHz, CDCl3): 4.32 (t, J ¼ 6.2,
2 H); 2.33 (t, J ¼ 7.5, 3 H); 1.63 – 1.61 (m, 6 H); 1.40 – 1.25 (m, 12 H); 0.97 – 0.89 (m, 21 H); 0.10 (d, J ¼
6.6, 12 H). 13C-NMR (75 MHz, CDCl3): 179.5; 85.6; 62.9; 38.7; 38.4; 33.9; 29.2; 29.1; 27.4; 25.8; 25.1; 24.6;
22.3; 18.2; 14.0; ꢀ 4.37; ꢀ 4.96. ESI-MS: 535 ([M þ Na]þ). HR-MS: 535.3636 ([M þ Na]þ,
C28H56O4NaSiþ2 ; calc. 535.3614).
(9S,12R)-9,12-Dihydroxyhexadec-10-ynoic Acid (2). As described for 1, from 20 (0.016 g, 58%): 2
(0.05 g, 0.09 mmol). Colorless liquid. [a]2D5 ¼ ꢀ8.3 (c ¼ 0.17, CD3OD). IR (KBr): 3381, 2928, 2895, 2857,
2020, 1710, 1549, 1459, 1408, 1330, 1075. 1H-NMR (300 MHz, CD3OD): 4.32 (t, J ¼ 6.5, 2 H); 2.27 (t, J ¼
7.3, 2 H); 1.71 – 1.55 (m, 6 H); 1.50 – 1.28 (m, 12 H); 0.93 (t, J ¼ 7.1, 3 H ) . 13C-NMR (75 MHz, CD3OD):