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HETEROCYCLES, Vol. 83, No. 6, 2011
+20.8° (c 1.00, CHCl3). FTIR (neat): 1729, 1472, 1374, 1281, 1216, 1158, 1071 cm-1. 1H NMR
(CDCl3): 1.25 (9H, s), 1.41 (3H, s), 1.43 (3H, s), 1.87 (2H, quint, J = 6.4 Hz), 2.25-2.37 (2H, m),
3.38-3.40 (1H, m), 3.57-3.68 (2H, m), 3.87 (1H, m), 4.03 (2H, q, J = 4.6 Hz), 4.15 (2H, t, J = 6.4 Hz),
5.06-5.14 (2H, m), 5.84 (1H, dt, J = 7.1, 10.0 Hz). 13C NMR (CDCl3): 25.3, 26.6, 27.1, 29.3, 35.5,
38.7, 61.2, 66.2, 66.8, 76.7, 79.6, 109.0, 117.4, 134.1, 178.4. EIMS m/z 314 (M+), 143 (100%).
HRMS (EI) calcd for C17H36O5 (M+) 314.2093, found 314.2080.
3-((2R,3S)-1,2-Dihydroxyhex-5-en-3-yloxy)propyl Pivalate (11): A solution of 10 (380 mg, 1.21
mmol) in 60% AcOH (15 mL) was stirred at rt for 8 h, basified with saturated NaHCO3, extracted with
CH2Cl2, washed with saturated NaCl, evaporated, and chromatographed on silica gel. Elution with
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n-hexane-AcOEt (3:2 then 1:1) gave 11 (311 mg, 94%) as a colorless oil. []D +19.1° (c 1.00,
CHCl3). FTIR (neat): 3437, 1725, 1287, 1166, 1107 cm-1. 1H NMR (CDCl3): 1.20 (9H, s), 1.88
(2H, quint, J = 6.1 Hz), 2.30-2.40 (3H, m), 2.79 (1H, m), 3.46-3.50 (2H, m), 3.66-3.78 (4H, m), 4.10
(1H, quint, J = 6.1 Hz), 4.27 (1H, quint, J = 6.1 Hz), 5.08-5.16 (2H, m), 5.78-5.88 (1H, m). 13C NMR
(CDCl3): 27.1, 29.3, 34.7, 61.1, 63.2, 66.4, 72.3, 80.5, 117.4, 134.2, 178.7. EIMS m/z 274 (M+), 143
(100%). HRMS (EI) calcd for C14H26O5 (M+) 274.1780, found 274.1762.
3-((S)-1-((R)-Oxiran-2-yl)but-3-enyloxy)propyl Pivalate (12): To a stirred solution of 11 (311 mg,
1.13 mmol) in 1,4-dioxane (11 mL) at rt, were added PPh3 (0.86 g, 3.4 mmol) and DEAD (40% in
toluene, 1.56 mL, 5.16 mmol). The resulting mixture was refluxed for 24 h, cooled to rt, evaporated,
and chromatographed on silica gel. Elution with n-hexane-AcOEt (10:1) gave 12 (206 mg, 71%) as a
26
colorless oil. []D +7.61° (c 1.00, CHCl3). IR (neat): 1724, 1476, 1284, 1161 cm-1. 1H NMR
(CDCl3): 1.20 (9H, s), 1.86 (2H, quint, J = 6.3 Hz), 2.30-2.44 (2H, m), 2.73-2.80 (2H, m), 2.94-2.96
(1H, m), 3.18-3.23 (1H, m), 3.46-3.52 (1H, m), 3.64-3.68 (1H, m), 4.14 (2H, t, J = 6.3 Hz), 5.07-5.16
(2H, m), 5.82-5.92 (1H, dt, J = 7.1, 10.3 Hz). 13C NMR (CDCl3): 27.1, 29.3, 37.0, 38.7, 45.3, 53.0,
61.2, 66.6, 78.4, 117.3, 133.9, 178.4. EIMS m/z 256 (M+), 143 (100%). HRMS (EI) calcd for
C14H24O4 (M+) 256.1675, found 256.1672.
3-((4S,5R)-5-Hydroxy-8-(trimethylsilyl)oct-1-en-7-yn-4-yloxy)propyl Pivalate (13): To a stirred
solution of trimethylsilylacetylene (423 l, 2.99 mmol) in THF (8 mL) at -78 °C, was added n-BuLi
(2.66 M solution in n-hexane, 1.0 mL, 2.66 mmol) and stirring was continued at -78 °C for 4 h. To the
stirred mixture at -78 °C, were added 12 (150 mg, 0.586 mmol) in THF (8 mL) and BF3-OEt2 (384 L,