10.1002/asia.201900421
Chemistry - An Asian Journal
FULL PAPER
added under N2 atmosphere and stirring was maintained at room
temperature for 40 min. The reaction was quenched with saturated aq.
NH4Cl (2 mL). The phases were separated and the organic layer was
diluted with EtOAc (30 mL), washed with brine, dried (Na2SO4) and
concentrated. The residue was purified by silica gel column
chromatography using petroleum ether/EtOAc (4:1) as eluent to afford 5a-
n.
CDCl3): 13.7, 22.2, 26.6, 33.1, 36.1, 58.0, 79.4, 82.3, 154.8 ppm. IR
(CHCl3): max = 3434, 2959, 2931, 2871, 1797, 1556, 1466, 1381, 1264,
1215, 1181, 1057, 914, 776, 754 cm-1. HRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C9H16O4Na 211.0941; Found 211.0959.
(4S,5S)-4-(2-Hydroxyethyl)-5-pentyl-1,3-dioxolan-2-one (5i). Prepared
using (DHQ)2-PHAL ligand in asymmetric dihydroxylation. Pale yellow oil
(0.501 g, 62%). [α]D25 = ‒32.7 (c = 1.0, CHCl3). 1H NMR (400 MHz, CDCl3):
0.87 (t, J = 6.9 Hz, 3H), 1.29‒1.49 (m, 6H), 1.63‒1.75 (m, 2H), 1.90‒1.96
(m, 2H), 2.53 (br s, 1H, OH), 3.81 (t, J = 5.5 Hz, 2H), 4.32‒4.37 (m, 1H),
4.46‒4.51 (m, 1H) ppm. 13C{1H} NMR (100 MHz, CDCl3): 13.8, 22.3, 24.2,
31.2, 33.4, 36.1, 58.0, 79.5, 82.3, 154.8 ppm. IR (CHCl3): max = 3458,
2955, 2932, 2864, 1801, 1654, 1552, 1464, 1381, 1175, 1061, 773, 668
cm-1. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C10H18O4Na 225.1097;
Found 225.1099. Following a similar procedure, racemic 5i was prepared
from 24i using catalytic pyridine instead of (DHQ)2-PHAL ligand, followed
by preparation of the carbonate. Analytical data is same as 5i. The
enantiomeric excess was determined by converting the triol 7i obtained
after asymmetric dihydroxylation of 23i into its tribenzoate 24i as
described below.
4-Benzyl-5-(2-hydroxyethyl)-1,3-dioxolan-2-one
(5a).
Colourless
semisolid (0.435 g, 49%). 1H NMR (400 MHz, CDCl3): 1.68‒1.76 (m, 1H),
1.83‒1.91 (m, 1H), 2.00 (br s, 1H, OH), 3.00 (dd, J = 14.2, 6.0 Hz, 1H),
3.11 (dd, J = 14.1, 6.2 Hz, 1H), 3.70 (t, J = 6.6 Hz, 2H), 4.55‒4.63 (m, 2H),
7.22‒7.24 (m, 2H), 7.28‒7.35 (m, 3H) ppm. 13C{1H} NMR (100 MHz,
CDCl3): 35.9, 39.2, 57.9, 78.8, 82.1, 127.4, 128.9, 129.4, 134.1, 154.4
ppm. IR (CHCl3): max = 3432, 2919, 2850, 1788, 1631, 1453, 1381, 1266,
1169, 1055, 755, 701, 465 cm-1. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd
for C12H14O4Na 245.0784; Found 245.0786.
4-(2-Hydroxyethyl)-5-(4-methylbenzyl)-1,3-dioxolan-2-one
(5b).
Colourless semisolid (0.482 g, 51%). 1H NMR (400 MHz, CDCl3): 1.68‒
1.76 (m, 1H), 1.83‒1.90 (m, 1H), 2.33 (s, 3H), 2.95 (dd, J = 14.3, 5.6 Hz,
1H), 3.07 (dd, J = 14.3, 5.7 Hz, 1H), 3.69‒3.72 (m, 2H), 4.53‒4.60 (m, 2H),
7.09‒7.15 (m, 4H) ppm. 13C{1H} NMR (100 MHz, CDCl3) 21.0, 36.0, 38.8,
58.0, 78.7, 82.2, 129.3, 129.6, 131.0, 137.2, 154.4 ppm. IR (CHCl3): max
= 3433, 2923, 1796, 1639, 1516, 1383, 1169, 1057, 808, 774, 697, 618,
526, 489 cm-1. LRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C13H16O4Na
259.0940; Found 259.0568.
(3S,4S)-Nonane-1,3,4-triyl tribenzoate (24i). To a stirred solution of
(3S,4S)-nonane-1,3,4-triol 7i (25 mg, 0.142 mmol) in pyridine (1.5 mL)
was added benzoyl chloride (0.17 mL, 1.43 mmol, 10.0 equiv) at 0 C. The
reaction mixture was stirred for 12 h and then quenched with ice water.
The solution was extracted with CHCl3 (2 10 mL). The combined organic
layers were concentrated and the residue purified by silica gel coloumn
chromatography using petroleum ether/EtOAc (19:1) to give the
tribenzoate 24i as colourless semisolid (59 mg, 85%).
4-(2-Hydroxyethyl)-5-(4-methoxybenzyl)-1,3-dioxolan-2-one
(5c).
Colourless semisolid (0.484 g, 48%). 1H NMR (400 MHz, CDCl3): 1.70‒
1.77 (m, 1H), 1.84‒1.92 (m, 1H), 2.95 (dd, J = 14.3, 5.7 Hz, 1H), 3.06 (dd,
J = 14.8, 5.7 Hz, 1H), 3.71‒3.74 (m, 2H), 3.79 (s, 3H), 4.54‒4.57 (m, 2H),
6.88 (d, J = 8.6 Hz, 2H), 7.14 (d, J = 8.7 Hz, 2H) ppm. 13C{1H} NMR (100
MHz, CDCl3): 36.0, 38.4, 55.3, 58.1, 78.6, 82.2, 114.3, 126.0, 130.5,
154.3, 159.0 ppm. IR (CHCl3): max = 3479, 2936, 2838, 1791, 1612, 1514,
1442, 1383, 1331, 1302, 1249, 1178, 1112, 1031, 904, 822, 774, 696, 617,
527 cm-1. LRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C13H16O5Na
275.0889; Found 275.0433.
25
1
[α]D = ‒0.8 (c = 0.25, CHCl3). H NMR (400 MHz, CDCl3): 0.81‒0.85
(m, 3H), 1.26‒1.38 (m, 4H), 1.39‒1.43 (m, 2H), 1.78‒1.79 (m, 2H), 2.24‒
2.27 (m, 2H), 4.36‒4.42 (m, 1H), 4.46‒4.54 (m, 1H), 5.46‒5.50 (m, 1H),
5.65‒5.69 (m, 1H), 7.36‒7.45 (m, 6H), 7.50‒7.57 (m, 3H), 7.98‒8.07 (m,
6H) ppm. 13C{1H} NMR (100 MHz, CDCl3): 13.9, 22.4, 24.9, 30.4, 30.7,
31.5, 61.2, 71.6, 74.6, 128.3, 128.4, 129.6, 129.66, 129.7, 129.8, 129.9,
132.9, 133.06, 133.1, 165.9, 166.1, 166.4 ppm. IR (CHCl3): max = 3063,
3032, 2955, 2928, 2857, 1720, 1602, 1584, 1491, 1451, 1378, 1314, 1268,
1176, 1108, 1070, 1026, 1001, 937, 913, 850, 803, 757, 711, 687, 617 cm-
1. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C30H32O6Na 511.2091; Found
511.2090. The racemic tribenzoate was prepared following similar
procedure. HPLC analysis: Chiralpak OD-H coloumn, hexane-iPrOH =
92:8, flow rate = 0.7 mL/min, tmajor = 9.90 min, 100% ee.
4-(4-Fluorobenzyl)-5-(2-hydroxyethyl)-1,3-dioxoan-2-one
(5d).
Pale
yellow semisolid (0.490 g, 51%). 1H NMR (400 MHz, CDCl3): 1.74‒1.82
(m, 1H), 1.87‒1.95 (m, 1H), 2.98‒3.09 (m, 2H), 3.73‒3.77 (m, 2H), 4.53‒
4.61 (m, 2H), 7.02 (t, J = 8.6 Hz, 2H), 7.18‒7.22 (m, 2H) ppm. 13C{1H} NMR
(100 MHz, CDCl3): 35.9, 38.4, 58.0, 78.7, 82.0, 115.76 (d, J = 21.4, Hz),
130.0 (d, J = 3.4, Hz), 131.0 (d, J = 8.0, Hz), 154.2, 162.2 (d, J = 247.9,
Hz) ppm. 19F NMR (470 MHz, CDCl3): ‒114.87 ppm. IR (CHCl3): max
3378, 2931, 1796, 1663, 1511, 1455, 1384, 1337, 1279, 1221, 1159, 1054,
826, 771 cm-1. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C12H13FO4Na
263.0690; Found 263.0690.
=
4-(3-Bromobenzyl)-5-(2-hydroxyethyl)-1,3-dioxoan-2-one (5e). Colourless
semisolid (0.650 g, 54%). 1H NMR (400 MHz, CDCl3): 1.68‒1.77 (m, 1H),
1.83‒1.91 (m, 1H), 2.16 (br s, 1H, OH), 3.00 (dd, J = 14.4, 5.4 Hz, 1H),
3.10 (dd, J = 14.4, 6.0 Hz, 1H), 3.69 (t, J = 5.8 Hz, 2H), 4.54‒4.63 (m, 2H),
7.22‒7.35 (m, 4H) ppm. 13C{1H} NMR (100 MHz, CDCl3): 35.9, 39.2, 57.9,
78.8, 82.1, 127.4, 128.6, 128.8, 129.3, 129.4, 134.2, 154.4 ppm. IR
(CHCl3): max = 3414, 2927, 2888, 1795, 1660, 1546, 1497, 1455, 1384,
1242, 1215, 1166, 1058, 756, 701 cm-1. LRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C12H13BrO4Na 303.0050; Found 303.1249.
4-(2-Hydroxyethyl)-5-hexyl-1,3-dioxolan-2-one (5j). Pale yellow oil (0.450
g, 52%). 1H NMR (500 MHz, CDCl3): 0.89 (t, J = 6.4 Hz, 3H), 1.26‒1.50
(m, 8H), 1.69‒1.73 (m, 2H), 1.95−2.01 (m, 2H), 3.85 (t, J = 4.9 Hz, 2H),
4.33‒4.37 (m, 1H), 4.47‒4.51 (m, 1H) ppm. 13C{1H} NMR (125 MHz,
CDCl3): 14.0, 22.4, 24.5, 28.8, 31.5, 33.5, 36.1, 58.2, 79.4, 82.2, 154.6
ppm. IR (CHCl3): max = 3433, 2952, 2928, 2857, 1796, 1464,1380, 1268,
1213, 1174, 1057, 903, 692, 666 cm-1. HRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C11H20O4Na 239.1254; Found 239.1257.
4-(2-Hydroxyethyl)-5-heptyl-1,3-dioxolan-2-one (5k). Pale yellow oil
(0.442 g, 48%). 1H NMR (500 MHz, CDCl3): 0.88 (t, J = 6.7 Hz, 3H),
1.24‒1.49 (m, 8H), 1.66‒1.78 (m, 4H), 1.92‒1.99 (m, 2H), 3.83‒3.85 (m,
2H), 4.33‒4.37 (m, 1H), 4.46‒4.50 (m, 1H) ppm. 13C{1H} NMR (125 MHz,
CDCl3): 14.0, 22.6, 24.6, 29.0, 29.1, 31.6, 33.5, 36.1, 58.2, 79.4, 82.2,
154.6 ppm. IR (CHCl3): max = 3485, 3018, 2926, 2855, 1801, 1655, 1465,
1379, 1349, 1180, 1056, 893, 695, 667, 620, 520, 488 cm-1. HRMS (ESI-
TOF) m/z: [M + Na]+ Calcd for C12H22O4Na 253.1410; Found 253.1412.
4-(2-Hydroxyethyl)-5-phenyl-1,3-dioxolan-2-one (5f). Pale yellow oil
(0.566 g, 68%). 1H NMR (400 MHz, CDCl3): 2.05 (q, J = 6.0 Hz, 2H), 2.80
(br s, 1H, OH), 3.76‒3.86 (m, 2H), 4.72 (q, J = 6.5 Hz, 1H), 5.33 (d, J = 7.6
Hz 1H), 7.34‒7.42 (m, 5H) ppm. 13C{1H} NMR (100 MHz, CDCl3): 35.3,
57.9, 81.7, 83.3, 126.1, 129.1, 129.7, 135.2, 154.5 ppm. IR (CHCl3): max
= 3433, 3020, 2918, 2849, 1805, 1498, 1458, 1376, 1353, 1279, 1186,
1159, 1069, 1050, 1027, 973, 699, 667, 626, 588, 496 cm-1. LRMS (ESI-
TOF) m/z: [M + Na]+ Calcd for C11H12O4Na 231.0627; Found 231.0729.
4-(2-Hydroxyethyl)-5-decyl-1,3-dioxolan-2-one (5l). Pale yellow oil (0.534
g, 49%). 1H NMR (400 MHz, CDCl3): 0.87 (t, J = 7.1 Hz, 3H), 1.25‒1.48
(m, 16H), 1.67‒1.73 (m, 2H), 1.91‒1.97 (m, 2H), 3.83 (t, J = 5.9 Hz, 2H),
4.34 (q, J = 6.6 Hz, 1H), 4.48 (q, J = 6.6 Hz, 1H) ppm. 13C{1H} NMR (125
MHz, CDCl3): 14.1, 22.6, 24.6, 29.1, 29.25, 29.3, 29.4, 29.5, 31.8, 33.5,
36.1, 58.1, 79.4, 82.2, 154.6 ppm. IR (CHCl3): max = 3482, 3018, 2925,
2855, 1794, 1561, 1465, 1379, 1344, 1181, 1058, 889, 760, 694, 667, 620,
536 cm-1. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C15H28O4Na 295.1880,
Found 295.1876.
5-Ethyl-4-(2-hydroxyethyl)-1,3-dioxolan-2-one (5g). Colourless oil (0.333 g,
52%). 1H NMR (400 MHz, CDCl3): 1.02 (t, J = 7.4 Hz, 3H), 1.72‒1.79 (m,
2H), 1.89‒1.96 (m, 2H), 2.57 (br s, 1H, OH), 3.79 (t, J = 6.5 Hz, 2H), 4.31
(q, J = 6.3 Hz, 1H), 4.47‒4.52 (m, 1H) ppm. 13C{1H} NMR (100 MHz,
CDCl3): 8.7, 26.5, 36.2, 57.9, 79.1, 83.3, 154.8 ppm. IR (CHCl3): max
=
3432, 2969, 2925, 2854, 1794, 1551, 1464, 1377, 1264, 1185, 1055, 910,
775, 734 cm-1. LRMS (ESI-TOF) m/z: [M + K]+ Calcd for C7H12O4K
199.0367; Found 199.0581.
4-(2-Hydroxyethyl)-5-butyl-1,3-dioxolan-2-one (5h). Pale yellow oil (0.496
g, 66%). 1H NMR (400 MHz, CDCl3): 0.90 (t, J = 6.7 Hz, 3H), 1.34‒1.45
(m, 4H), 1.66‒1.77 (m, 2H), 1.90‒1.96 (m, 2H), 3.81 (t, J = 5.3 Hz, 2H),
4.32‒4.37 (m, 1H), 4.46‒4.51 (m, 1H) ppm. 13C{1H} NMR (100 MHz,
(3R,4R)-4-(2-Hydroxyethyl)-5-hexadecyl-1,3-dioxolan-2-one
(5m).
Prepared using (DHQD)2-PHAL ligand in asymmetric dihydroxylation.
White solid (0.813 g, 57%), m.p. = 48‒50 C. [α]D25 = +15.4 (c = 0.3, CHCl3).
1H NMR (500 MHz, CDCl3): 0.87 (t, J = 6.6 Hz, 3H), 1.24‒1.48 (m, 26H),
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