P. Chen, S. Wang / Tetrahedron 68 (2012) 5356e5362
5361
a
:
b
¼100:9) {lit.:4k
½
a 3D1:7
ꢂ
¼þ115.3 (c 1.0, CHCl3,
a
:
b
¼7:3)}; 1H NMR
m/z: 370(Mþ,3), 237(3), 213(5), 157(3), 143(12), 142(100), 141(84),
140(8), 127(6), 115(15), 111(18), 81(6), 43(41).
(400 MHz, CDCl3):
d
0.96(t, J¼7.3 Hz, 3H), 1.38e1.44(m, 2H),
1.57e1.62(m, 2H), 2.09(s, 3H), 2.11(s, 3H), 3.50e3.56(m, 1H),
3.77e3.88(m, 1H), 4.10e4.14(m,1H), 4.17e4.28(m,2H), 5.04(s,1H),
5.32(d, J¼9.6.1H), 5.83e5.96(m,2H) ppm; IR (film, cmꢃ1):3043,
2974, 2847, 1743, 1442, 1370, 1229, 1107, 1048, 980, 906, 726, 596,
489; MS(ESI) m/z: 595.2 ([2MþNa]þ,10), 309.1 ([MþNa]þ,100),
213.1(23),153.1(8).
4.2.11. (2-Thienyl)-methyl 4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-
hex-2-enopyranoside (3k). Colorless oil; ½a D25
ꢂ ¼þ82 (c 0.62, CHCl3,
a
only); 1H NMR(400 MHz, CDCl3):
d 2.09 (s, 3H), 2.13 (s, 3H),
4.07e4.35 (m, 3H), 4.82 (d, J¼12.4 Hz, 1H), 4.93 (d, J¼12.4 Hz, 1H),
5.17 (s, 1H), 5.35 (d, J¼9.3 Hz, 1H), 5.87 (dd, J¼30.4, 10.2 Hz, 2H),
6.94e7.10 (m, 2H), 7.32 (d, J¼5.0 Hz, 1H) ppm; IR (film, cmꢃ1):3063,
2937, 2358, 1740, 1531, 1446, 1364, 1323, 1228, 1180, 1135, 1094,
4.2.5. sec-Butyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
enopyranoside (3e). Colorless oil;
½
a 2D5
ꢂ
¼þ134 (c 0.63, CHCl3,
1024, 972, 898, 845, 706, 600. 13C NMR(101 MHz, CDCl3):
d 20.82,
a:
b
¼10:1) {lit.:7e
(
a
:
b
¼11:1)}; 1H NMR(400 MHz, CDCl3):
20.96, 53.40, 62.92, 64.35, 66.28, 67.20, 93.07, 126.22, 126.79,
127.03, 127.60, 129.45, 170.25, 170.77 ppm. MS(ESI) m/z: 349.0
([MþNa]þ,100), 283.3(34), 213.3 (14); HR-ESI C15H18O6SNa
[MþNa]þ Calcd: 349.0716, Found 349.0719.
d
0.93(dt, J¼18.9, 7.4 Hz, 3H), 1.15(d, J¼6.2 Hz, 2H), 1.25(d, J¼6.3 Hz,
1H), 1.47e1.59(m,2H), 2.09(s, 3H), 2.10(s, 3H), 3.70e3.80(m, 1H),
4.16e4.23(m, 3H), 5.13(dd,J¼4.0,2.9 Hz, 1H), 5.30(dd, J¼9.6,1.4 Hz,
1H), 5.78e5.86(m, 2H) ppm; IR (film, cmꢃ1):3053, 2956, 2880,1745,
1452, 1373, 1233, 1102, 1042, 901, 730; MS(ESI) m/z: 595.2(
[2MþNa]þ, 8), 309.1( [MþNa]þ, 100), 213.1(20), 153.1(10).
4.2.12. 1-Trifluoromethyl-1-(2-nitro-5-chlorophenyl)-methyl 4,6-di-
O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-enopyranoside
(3l). Pale
yellow solid; Mp 52 ꢀC; ½a D25
ꢂ
¼þ115 (c 0.41, CHCl3,
a
only); 1H NMR
4.2.6. tert-Butyl 4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-
(400 MHz, CDCl3: d 2.15(s, 3H), 2.18(s, 3H), 3.57e3.74 (m, 1H),
enopyranoside (3f). Colorless oil;
½
a 2D5
ꢂ
¼þ126 (c 0.72, CHCl3,
3.99e4.03(m, 1H), 4.24e4.27(m, 1H), 4.99(s, 1H), 5.33 (dd, J¼13.1,
4.7 Hz, 1H), 5.82e6.12 (m, 2H), 6.43 (q, J¼6.1 Hz, 1H), 7.60 (ddd,
J¼8.8, 4.2, 2.3 Hz, 1H), 7.89 (dd, J¼21.3, 1.9 Hz, 1H), 8.10 (dd, J¼8.8,
1.6 Hz, 1H) ppm; IR (film, cmꢃ1): 2923, 2851, 2361, 1745, 1575, 1531,
1462,1370,1231,1183,1140,1090,1046, 977, 902, 853, 698; 13C NMR
a 25
a
only) {lit.:7c ½ ꢂD ¼þ100.69(c 0.75, CHCl3)}; 1H NMR(400 MHz,
CDCl3):
d 1.28(s, 9H), 2.06(s, 3H), 2.07(s, 3H), 4.12e4.24(m,3H),
5.25 (dd,J¼9.0, 1.3 Hz, 1H), 5.31 (d, J¼2.1 Hz, 1H), 5.71e5.84(m, 2H)
ppm; IR (film, cmꢃ1):3051, 2975, 2722, 1746, 1436, 1369, 1195, 1099,
1043, 982, 892, 774; MS(ESI) m/z: 595.2( [2MþNa]þ,8),309.1
([MþNa]þ,100), 213.1(30), 153.1(15).
(101 MHz, CDCl3):
64.99, 67.89, 92.50, 125.80, 126.63, 126.95, 129.87, 130.36, 131.21,
140.68, 170.26, 170.93 ppm; 19F NMR(282 MHz, CDCl3):
d 20.68, 20.98, 30.99, 62.04, 62.59, 64.74,
d
:
4.2.7. Cyclohexyl 4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-
ꢃ75.54(d, J¼6.5 Hz), ꢃ75.89(d, J¼6.3 Hz) ppm; MS(ESI) m/z:
enopyranoside (3g). Colorless oil;
½
a 2D5
¼þ110.7 (c 1.0, CHCl3
ꢂ
¼þ162 (c 0.58, CHCl3,
490.0([MþNa]þ,
100),
213.1(13),
153.1(8);
HR-ESI
a:b
¼20:1) {lit.:4k
½
a 3D1:7
ꢂ
a
:
b
¼9:1)}; 1H NMR
C18H17ClF3NO8Na [MþNa]þ Calcd 490.0493, Found 490.0497.
(400 MHz, CDCl3):
d 1.11e1.20(m, 5H), 1.46e1.49(m, 1H),
1.67e1.71(m, 2H), 1.81e1.90(m, 2H), 2.01(s, 3H), 2.02(s, 3H),
3.54e3.60(m, 1H), 4.11e4.18(m, 3H), 5.10(s, 1H), 5.21(dd, J¼9.2,
1.5 Hz, 1H), 5.73e5.81(m, 2H) ppm; IR (film, cmꢃ1):3055, 2934,
2857, 1744, 1450, 1371, 1233, 1101, 1036, 742, 606; MS(EI 70 eV) m/z:
313(Mþþ1), 213(24), 210(16), 168(23), 153(36), 128(27), 111(73),
86(58), 55(28), 43(100), 41(15).
4.2.13. 6-O-(4,6-Di-O-acetyl-2,3-dideoxy-
a
-
D
-erythreo-hex-2-
enopyranosyl)-1,2:3,4-di-O-isopropylidene-a-D-galactopyranose
(3n). White solid; Mp 132e134 ꢀC; ½a D25
ꢂ ¼þ9 (c 0.75, CHCl3,
a
:
b
¼8:1), {lit:7d mp 137 ꢀC ½a 2D5
ꢂ
¼þ16.8(c 1.0, CHCl3
a:b
¼5:1)}; 1H
NMR(400 MHz, CDCl3): d 1.34 (s, 3H),1.36(s, 3H),1.45 (s, 3H),1.54
(s, 3H), 2.09 (s, 3H) 2.12 (s, 3H), 3.73e3.79 (m, 1H), 3.86e3.91 (m,
1H), 4.00e4.04(m, 1H), 4.12e4.18(m, 2H), 4.23e4.34(m, 3H), 4.63
(d, J¼7.8 Hz,1H), 5.10(s,1H), 5.33 (d, J¼9.8 Hz,1H), 5.54 (d, J¼4.9 Hz,
1H), 5.84e5.91 (m, 2H) ppm. IR (film, cmꢃ1): 2998, 2930, 2365,
1742, 1580, 1456, 1377, 1227, 1049, 1003, 967, 892, 677; MS(ESI) m/z:
495.0 ([MþNa]þ,100); 256.0(10).
4.2.8. Cyclopropylmethyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-
hex-2-enopyranoside (3h). Colorless oil; ½a D25
ꢂ ¼þ144 (c 0.67, CHCl3,
a:
b
¼5:1) {lit.:7a
½
a 2D5
ꢂ
¼þ105.6 (c 1.45, CHCl3
a
:
b
¼7:1)}; 1H NMR
(400 MHz, CDCl3):
d 0.28e0.15 (m, 2H), 0.53e0.57(m, 2H),
1.07e1.12(m, 1H), 2.08(s, 6H), 3.41e3.53(m, 2H), 4.11e4.18(m, 3H),
5.07(s, 1H), 5.30 (d, J¼9.6 Hz, 1H), 5.83e5.96(m, 2H) ppm; IR (film,
cmꢃ1):3078, 2945, 1744, 1437, 1374, 1230, 1094, 1040, 967, 906, 830,
730, 677; MS(ESI) m/z :307.1([MþNa]þ,100) 213.1(20), 153.1(8).
4.2.14. Epiandrosteronyl-4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-
hex-2-enopyranoside (3o). White solid; Mp 124e126 ꢀC;
½
a 2D5
ꢂ
¼þ105 (c 0.53, CHCl3,
a
:b
¼9:1); 1H NMR (400 MHz, CDCl3):
d
0.69 (dd, J¼16.3, 6.0 Hz,1H), 0.84(s, 3H), 0.87(s, 3H), 0.94e1.92 (m,
4.2.9. Benzyl 4,6-di-O-acetyl-2,3-dideoxy-
enopyranoside (3i). Colorless oil;
a 2D5
only) {lit.:4k
a 3D1:7
¼þ56.34 (c 1.0, CHCl3
(400 MHz, CDCl3):
a
-
D
-erythro-hex-2-
20H), 2.09 (s, 3H), 5.21(s, 1H), 2.11 (s, 3H), 2.45 (dd, J¼19.2, 8.8 Hz,
1H), 3.83e3.51 (m, 1H), 4.31e4.10 (m, 3H), 5.18 (s, 1H), 5.32 (d,
J¼9.6 Hz, 1H), 5.98e5.73 (m, 2H) ppm; IR (film, cmꢃ1): 2934, 2855,
1743, 1635, 1454, 1374, 1232, 1035, 910, 829, 744, 653; 13C NMR
½
ꢂ ¼þ96 (c 0.56, CHCl3
,
a
½
ꢂ
a
:b
¼9:1)}; 1H NMR
d
2.10(s, 3H), 2.11(s, 3H), 4.12e4.32(m, 3H),
4.62 (d, J¼11.7 Hz, 1H). 4.83 (d, J¼11.7 Hz, 1H), 5.16 (s, 1H), 5.36 (d,
J¼9.3 Hz, 1H), 6.03e5.85 (m, 2H), 7.35e7.40(m, 5H) ppm; IR (film,
cmꢃ1): 3062, 2903, 1746, 1606, 1496, 1453, 1371, 1235, 1186, 1101,
1040, 735, 535, 478; MS(EI 70 eV) m/z: 319(Mþꢃ1), 213(7), 187(8),
176(9), 153(8), 111(26), 109(8), 94(19), 91(100), 81(8), 65(7), 43(69).
(101 MHz, CDCl3): d 12.23, 13.82, 20.48, 20.83, 20.99, 21.78, 28.09,
28.55, 30.91, 30.94, 31.55, 35.05, 35.75, 35.85, 36.26, 36.92, 45.11,
47.80, 51.40, 54.45, 63.19, 65.35, 66.77, 77.77, 93.07, 128.42, 128.86,
170.33, 170.81 ppm; MS(ESI) m/z: 525.1 ([MþNa]þ,100), 212.9(10);
HR-ESI C29H42O7Na [MþNa]þ Calcd 525.2828, found 525.2823.
4.2.10. (2-Naphthyl)-methyl
4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-er-
4.2.15. 16-Dehydropregnenolonyl-4,6-di-O-acetyl-2,3-dideoxy-
erythro-hex-2-enopyranoside (3p). White solid; Mp 70e72 ꢀC;
a 2D5
¼þ174 (c 0.6, CHCl3,
only); 1H NMR(400 MHz, CDCl3):
0.92 (s, 3H), 0.99e1.08(m, 5H), 1.24e2.06(m, 12H), 2.08 (s, 3H),
2.10 (s, 3H), 2.26 (s, 3H), 2.37 (dd, J¼25.4, 11.5 Hz, 3H), 3.56 (dd,
J¼13.5, 8.6 Hz, 1H), 4.18e4.27(m, 3H), 5.18(s, 1H), 5.30 (d, J¼9.3 Hz,
1H), 5.37 (s, 1H), 5.85 (dd, J¼23.2, 10.4 Hz, 2H), 6.71 (s, 1H) ppm; IR
(film, cmꢃ1): 3043,2939, 2859, 1745, 1666, 1576, 1442, 1372, 1232,
a-D-
ythro-hex-2-enopyranoside (3j). Colorless solid; Mp 73 ꢀC,
½
a 2D5
CHCl3 a
ꢂ
¼þ97.5 (c 1.6, CHCl3,
a
only) {lit.:7b mp 72 ꢀC,½a 2D3
ꢂ
¼þ12(c 1.0,
½
ꢂ
a
:
b
¼9:1)}; 1H NMR(400 MHz, CDCl3):
d
2.11(s, 3H), 2.12(s,
d
3H), 4.17e4.31(m, 3H), 4.79 (d, J¼11.8 Hz, 1H), 4.99 (d, J¼11.8 Hz,
1H), 5.21(s, 1H), 5.37 (dd,J¼9.3, 1.3 Hz, 1H), 5.90e5.95(m, 2H),
7.44e7.58 (m, 3H), 7.84e7.87(m, 4H) ppm; IR (film, cmꢃ1): 3054,
2933, 2876,1737, 1375, 1236,1046,1021, 859, 821, 752; MS(EI 70 eV)