Helvetica Chimica Acta – Vol. 91 (2008)
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(2S,3R,4E,6Z)-2-Acetamide-1,3-bis(benzyloxy)octadeca-4,6-diene (¼ N-[(2S,3R,4E,6Z)-1,3-Bis-
(benzyloxy)octadeca-4,6-dien-2-yl]acetamide; 10). Compound 10 was obtained according to the
procedure described for the synthesis of 7. 1H-NMR (CDCl3, 300 MHz): 7.31 – 7.25 (m, 10 H); 6.50
(dd, J ¼ 10.8, 14.7, 1 H); 6.00 (t, J ¼ 10.5, 1 H); 5.73 (d, J ¼ 9.0, 1 H); 5.63 – 5.44 (m, 2 H); 4.64 (d, J ¼ 12.0,
1 H); 4.60 (d, J ¼ 11.7, 1 H); 4.50 (d, J ¼ 11.7, 1 H); 4.30 (d, J ¼ 11.7, 1 H); 4.29 – 4.22 (m, 1 H); 4.01 (t, J ¼
7.5, 1 H); 3.81 (dd, J ¼ 7.5, 9.9, 1 H); 3.55 (dd, J ¼ 3.9, 9.6, 1 H); 2.18 – 2.13 (m, 2 H); 1.89 (s, 3 H); 1.25 (br.
s, 18 H); 0.87 (t, J ¼ 6.9, 1 H). 13C-NMR (CDCl3, 75 MHz): 169.5; 138.3; 138.0; 133.5; 130.1; 129.9; 128.4;
127.8; 127.6; 127.4; 79.3; 77.3; 73.1; 70.4; 68.4; 51.9; 31.9; 29.6; 29.5; 29.33; 29.3; 27.8; 23.4; 22.7. HR-ESI-
MS: 542.3605 ([M þ Na]þ, C34H49NNaO3þ ; calc. 542.3610).
(2S,3S,4R)-N,O,O,O-Tetraacetyl-d-ribo-phytosphingosine (¼ N-{(1S,2S,3R)-2,3-Bis(acetyloxy)-1-
[(acetyloxy)methyl]heptadecyl}acetamide; 11). MethodA . Compound 6 (18 mg, 0.029 mmol) and 10%
Pd/C (20.0 mg) in MeOH (6.0 ml), AcOEt (3.0 ml), and AcOH (1.0 ml) were stirred for 4 d under H2.
The catalyst was then removed by filtration through Celite, and the filtrate was concentrated. The residue
was dissolved in pyridine (5.0 ml), Ac2O (1.0 ml) was added, and the mixture was stirred for 4 h. The
mixture was concentrated. CC (petroleum ether/AcOEt 2 :1) of the residue provided product 11 (13 mg,
1
92%) as a white solid. H-NMR (CDCl3, 500 MHz): 5.92 (d, J ¼ 9.5, 1 H); 5.10 (dd, J ¼ 3.0, 8.5, 1 H);
4.95 – 4.92 (m, 1 H); 4.50 – 4.44 (m, 1 H); 4.29 (dd, J ¼ 5.0, 11.5, 1 H); 4.00 (dd, J ¼ 3.0, 11.5, 1 H); 2.06 (s,
3 H); 2.03 (s, 6 H); 2.00 (s, 3 H); 1.78 – 1.58 (m, 2 H); 1.24 (br. s, 26 H); 0.88 (t, J ¼ 7.0, 3 H). The
spectroscopic data coincide with those reported previously [17].
MethodB. Compound 7 (50 mg, 0.08 mmol) and 10% Pd/C (10.0 mg) in MeOH (8.0 ml) and AcOEt
(4.0 ml) were stirred for 2 d under H2. The catalyst was then removed by filtration through Celite, and the
filtrate was concentrated. The residue was dissolved in pyridine (2 ml) and Ac2O (1 ml), and the mixture
was stirred for 6 h. The mixture was concentrated. CC (petroleum ether/AcOEt 2 :1) of the residue
provided product 11 (42 mg, 98%).
(2S,3R)-N,O,O-Triacetyl-d-erythro-dihydrosphingosine (¼ N-[(1S,2R)-2-(Acetyloxy)-1-[(acetyl-
oxy)methyl]heptadecyl]acetamide; 12). Compound 12 was obtained in 95% yield according to the
1
procedure described for the synthesis of 11, MethodB . H-NMR (CDCl3, 500 MHz): 5.85 (d, J ¼ 9.5,
1 H); 4.95 (dt, J ¼ 5.0, 10.5, 1 H); 4.42 – 4.36 (m, 1 H); 4.25 (dd, J ¼ 5.0, 11.5, 1 H); 4.06 (dd, J ¼ 3.5, 11.5,
1 H); 2.07 (s, 3 H); 2.06 (s, 3 H); 2.00 (s, 3 H); 1.65 – 1.52 (m, 2 H); 1.33 – 1.24 (br. s, 26 H); 0.88 (t, J ¼ 7.0,
3 H). The spectroscopic data coincide with those reported previously [18].
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