Helvetica Chimica Acta – Vol. 97 (2014)
1331
(1S,5R)-1,5-Anhydro-2-deoxy-3,4-O-(1-methylethylidene)-5-(2-oxopropyl)-1-propyl-d-threo-penti-
tol (12). To a soln. of 10 (0.65 g, 1.8 mmol) in THF (4 ml) was added HF/pyridine (1.8 ml, 1.8 mmol) at 08.
After stirring the mixture for 3 h at r.t., the reaction was quenched with sat. aq. NaHCO3 soln. (10 ml).
The aq. layer was extracted with AcOEt (2 ꢁ 5 ml). The combined org. phases were dried (Na2SO4), and
concentrated in vacuo. The residue was purified by CC (SiO2) to afford alcohol 11 (0.4 g, 90%) as a pale-
yellow liquid. To a stirred soln. of alcohol 11 (0.100 g, 0.41 mmol) in MeCN (10 ml) were added LiCl
(0.173 g, 4.1 mmol) and DBU (0.62 g, 4.1 mmol) at r.t. After stirring at the same temp. for 1.5 h, the
reaction was quenched with sat. aq. NH4Cl soln., and the mixture was extracted with Et2O. The combined
extracts were washed with brine, dried (MgSO4), filtered, and concentrated in vacuo. The residue was
purified by CC to afford pure 12 (0.09 g, 90%). Colorless liquid. Rf (AcOEt/hexane 3 :7) 0.5. Rf (AcOEt/
hexane 1:9) 0.8. [a]2D7 ¼ þ9.58 (c ¼ 1.0, CHCl3). IR (KBr): 2956, 2928, 1684, 1364, 1179, 1035, 833, 773.
1H-NMR (CDCl3, 300 MHz): 0.90 (t, J ¼ 7.3, 3 H); 1.20 – 1.62 (m, 11 H); 2.11 (td, J ¼ 6.5, 4.1, 1 H); 2.21 (s,
3 H); 2.76 – 2.61 (m, 2 H); 3.04 (t, J ¼ 8.8, 1 H); 3.38 – 3.49 (m, 1 H); 3.54 – 3.62 (m, 1 H); 3.91 (dt, J ¼ 8.5,
4.1, 1 H). 13C-NMR (CDCl3, 75 MHz):13.7; 18.6; 26.8; 30.7; 37.4; 38.9; 46.5; 73.2; 75.4; 76.4; 78.1; 79.8;
109.6; 208.2. HR-ESI-MS: 279.1571 ([M þ Na]þ, C14H24NaO4þ ; calc. 279.1566).
Phomonol (¼(1S,5R)-1,5-Anhydro-2-deoxy-5-(2-oxopropyl)-1-propyl-d-threo-pentitol; 1). A mix-
ture of 12 (0.09 g, 0.35 mmol) and CeCl3 · 7 H2O (0.39 g, 1.05 mmol) in MeCN (5 ml) was stirred at reflux
temp. for a specified time as required to complete the reaction. After completion of the reaction (TLC),
the mixture was extracted with AcOEt, and the combined org. layers were washed with H2O and brine,
dried (Na2SO4), and concentrated under reduced pressure to remove the solvent. The crude product was
purified by CC to afford pure 1 (0.05 g, 66%). Colorless liquid. Rf (AcOEt/hexane 3 :7) 0.5. [a]2D7 ¼ þ10.2
(c ¼ 1.0, CHCl3). IR (KBr): 3368, 2966, 2924, 1686, 1365, 1248, 1036, 843, 778. 1H-NMR (CDCl3,
300 MHz): 0.91 (t, J ¼ 7.4, 3 H); 1.29 – 1.42 (m, 4 H); 1.44 – 1.54 (m, 1 H); 2.00 (ddd, J ¼ 12.4, 5.5, 2.1,
1 H); 2.22 (s, 3 H); 2.69 (dd, J ¼ 15.4, 7.5, 1 H); 2.88 (dd, J ¼ 15.6, 4.5, 1 H); 3.10 (t, J ¼ 8.4, 1 H); 3.38 –
3.48 (m, 1 H); 3.58 – 3.69 (m, 2 H). 13C-NMR (CDCl3, 75 MHz): 14.0; 18.8; 31.1; 37.6; 39.0; 46.6; 73.2;
75.6; 75.4; 76.3; 208.4. HR-ESI-MS: 239.1258 ([M þ Na]þ, C11H20NaO4þ ; calc. 239.1253).
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