The Journal of Organic Chemistry
Page 12 of 17
(2S,4S)-16-(Dimethyl(phenyl)silyl)heptadec-16-ene-1,2,4-triol (ent-24). Compound ent-1 (61 mg, 0.21 mmol) was treated as described
for conversion of 1 into 24 to afford ent-24 (87 mg, 97%) as a colourless oil: [a]D +3.9 (c 0.3, CHCl3); HRMS (ESI) m/z calcd for
C25H44NaO3Si [M + Na]+ 443.2952, found 443.2949. The IR and NMR data for ent-24 was the same as that for 24.
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(2R,4S)-16-(Dimethyl(phenyl)silyl)heptadec-16-ene-1,2,4-triol (25). Compound 23 (64 mg, 0.23 mmol) was treated as described for the
conversion of 1 into 24 to afford 25 (91 mg, 95%) as a colourless oil: Rf = 0.38 (95:5 EtOAc–CH3OH); [a]D +2.6 (c 0.3, CHCl3); IR (cast
film): 3326, 3069, 3050, 3027, 2925, 2853, 1466, 1428, 1248, 1111, 1077 cm–1; 1H NMR (700 MHz, CDCl3) δ 7.53–7.49 (m, 2H), 7.36–
7.32 (m, 3H), 5.67 (dt, J = 3.2, 1.6 Hz, 1H), 5.39 (app d, J = 3.0 Hz, 1H), 4.03 (app tt, J = 7.2, 3.4 Hz, 1H), 3.96–3.89 (m, 1H), 3.66 (dd, J =
11.0, 3.4 Hz, 1H), 3.54 (dd, J = 11.0, 7.2 Hz, 1H), 2.92 (br s, 1H), 2.21–2.06 (m, 4H), 1.69 (ddd, J = 14.5, 8.6, 2.8 Hz, 1H), 1.58–1.15 (m,
21H), 0.36 (s, 6H); 13C{1H} NMR (176 MHz, CDCl3) δ 150.6, 138.6, 134.0, 128.9, 127.7, 125.7, 69.7, 69.5, 67.0, 38.9, 37.7, 36.1, 29.7,
29.64, 29.63, 29.62, 29.53, 29.47, 28.9, 25.8, –2.8; HRMS (ESI) m/z calcd for C25H44NaO3Si [M + Na]+ 443.2952, found 443.2952.
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(2S,4R)-16-(Dimethyl(phenyl)silyl)heptadec-16-ene-1,2,4-triol (ent-25). Compound ent-23 (55 mg, 0.19 mmol) was treated as described
for the conversion of 1 into 24 to afford ent-25 (75 mg, 92%) as a colourless oil.: [a]D –3.0 (c 0.3, CHCl3); HRMS (ESI) m/z calcd for
C25H44NaO3Si [M + Na]+ 443.2952, found 443.2951. The IR and NMR data for ent-25 was the same as that for 25.
(2R,4R)-Heptadec-16-ene-1,2,4-triol (2). Vinylsilane 24 (76 mg, 0.18 mmol) was dissolved in DMF (1.8 mL) and TBAF (1.0 M in THF,
0.90 mL, 0.90 mmol) was added. The mixture was heated to 80 ºC for 15 h, cooled to room temperature and then the solvent was removed
under reduced pressure. The crude mixture was purified by silica gel flash chromatography (95:5 EtOAc–CH3OH) to afford 2 (48 mg, 92%)
as a white solid: Rf = 0.42 (95:5 EtOAc–CH3OH); mp 63–64 ºC (lit.8 66.5–67 ºC); [a]D –5.4 (c 0.5, CHCl3) [lit.8 –6.4 (c 1.1, CHCl3)]; IR
(cast film): 3301, 3082, 2923, 2851, 1641, 1471, 1216, 1134, 1068, 909, 758 cm–1; 1H NMR (700 MHz, CD3OD) δ 5.80 (ddt, J = 17.0, 10.2,
6.8 Hz, 1H), 4.99–4.95 (m, 1H), 4.90 (ddt, J = 10.2, 2.0, 1.2 Hz, 1H), 3.83–3.72 (m, 2H), 3.49 (dd, J = 11.2, 4.6 Hz, 1H), 3.45 (dd, J = 11.2,
6.0 Hz, 1H), 2.07–2.00 (m, 2H), 1.65 (app dt, J = 14.1, 4.5 Hz, 1H), 1.56–1.20 (m, 21H); 13C{1H} NMR (176 MHz, CD3OD) δ 140.2, 114.7,
72.2, 71.2, 67.3, 41.2, 38.7, 34.9, 30.84, 30.76, 30.75, 30.7, 30.6, 30.2, 30.1, 26.6; HRMS (ESI) m/z calcd for C17H34NaO3 [M + Na]+
309.2400, found 309.2401.
(2S,4S)-Heptadec-16-ene-1,2,4-triol (ent)-2. Compound ent-24 (72 mg, 0.17 mmol) was treated as described for the conversion of 24 into
2 to afford ent-2 (44 mg, 91%) as a white solid: mp 63–64 ºC (lit.8 65.5–66 ºC); [a]D +5.0 (c 0.5, CHCl3) [lit.8 +6.0 (c 1.0, CHCl3)]; HRMS
(ESI) m/z calcd for C17H34NaO3 [M + Na]+ 309.2400, found 309.2399. The IR and NMR data for ent-2 was the same as that for 2.
(2R,4S)-Heptadec-16-ene-1,2,4-triol (26). Compound 25 (90 mg, 0.21 mmol) was treated as described for the conversion of 24 into 2 to
afford 26 (54 mg, 89%) as a white solid: Rf = 0.33 (95:5 EtOAc–CH3OH); mp 79–81 ºC (lit.8 82–82.5 ºC); [a]D +3.7 (c 0.5, CHCl3) [lit.8
+7.23 (c 0.83, CHCl3)]; IR (cast film): 3256, 2916, 2848, 1643, 1469, 1076, 1031, 989, 913 cm–1; 1H NMR (700 MHz, CD3OD) δ 5.80 (ddt,
J = 17.0, 10.2, 6.7 Hz, 1H), 5.00–4.94 (m, 1H), 4.92–4.88 (m, 1H), 3.87–3.83 (m, 1H), 3.81–3.76 (m, 1H), 3.47 (dd, J = 11.1, 4.8 Hz, 1H),
3.43 (dd, J = 11.1, 6.4 Hz, 1H), 2.06–2.00 (m, 2H), 1.52–1.23 (m, 22H); 13C{1H} NMR (176 MHz, CD3OD) δ 140.2, 114.7, 70.4, 69.1, 67.9,
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