16
A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
97–98 °C, lit.19 98 °C, ½a D22
ꢀ
ꢁ26 (c 0.15, CHCl3); lit.19 ꢁ25 (c 0.1,
170.3, 169.9, 169.8 (COCH3); 162.9 (Cqv); 145.1 (Aryl-C); 142.4
(Cqv); 130.7, 125.1 (Aryl-C); 80.7 (C-1); 75.9 (C-5); 71.6 (C-4);
67.2 (C-3); 67.1 (C-2); 61.3 (C-6), 20.7, 20.6, 20.5 (OCOCH3); 77Se
NMR (CDCl3, 95.4 MHz): d495. Anal. Calcd for C19H22N2O11Se: C,
51.76; H, 5.49. Found: C, 51.66; H 5.70. HRMS m/z Calcd for:
CH2Cl2); 1H NMR (CDCl3, 500 MHz): d 7.62 (d, 2H, Aryl-H); 7.42–
7.32 (m, 3H, Aryl-H); 5.20 (t, 1H, H-2, J2,3 9.2 Hz); 5.05 (t, 1H, H-
3, J3,4 9.8 Hz); 5.02 (t, 1H, H-4, J4,5 9.3 Hz); 4.90 (d, 1H, H-1, J1,2
10.2 Hz); 4.22–4.16 (overlapping signals, 2H, H-6a, H-6b); 3.71
(m, 1H, H-5); 2.10, 2.08, 2.06 (s, 12H, 4 ꢂ OCOCH3); 13C NMR
(CDCl3, 125 MHz): d 170.5, 170.2, 169.4, 169.3 (COCH3); 135.3,
129.0, 128.6 (Aryl-C); 126.9 (Cqv.); 80.9 (C-1); 76.9 (C-5); 73.8 (C-
2); 70.7 (C-3); 68.1 (C-4); 62.1 (C-6), 20.8, 20.7, 20.6 (COCH3);
77Se NMR (CDCl3, 95.4 MHz): d 420. Anal. Calcd for C20H24O9Se:
C, 49.30; H, 4.96. Found: C, 49.35; H, 5.13. HRMS m/z Calcd for
C
19H22N2O11Se [M+Na]+: 557.039. Found: 557.031.
3.2.40. (5-Nitropyrid-2-yl) 2-acetamido-2-deoxy-3,4,6-tri-O-
acetyl-1-seleno-b- -glucopyanoside (41)
From 4 (100 mg, 0.20 mmol), 2-chloro-5-nitropyridine (5m,
D
33 mg, 0.20 mmol) and Et3N (29 lL, 0.22 mmol), 95 mg (87%), so-
C
20H24O9Se [M+Na]+: 511.048. Found: 511.048.
lid, mp 197–199 °C, ½a D22
ꢀ
ꢁ2 (c 0.2, CDCl3); 1H NMR (CDCl3,
500 MHz): d 9.24 (d, 1H, Aryl-H); 8.24 (dd, 1H, Aryl-H); 7.51 (dd,
1H, Aryl-H); 6.02 (dd, 1H, NH); 5.88 (dd, 1H, H-1, J1,2 10.8 Hz);
5.21 (overlapping signals, 2H, H-3, H-4); 4.49 (m, 1H, H-2); 4.26
(dd, 1H, H-6a, J5,6a 2.0 Hz, J6a,6b 12.5 Hz); 4.05 (d, 1H, H-6b, J5,6b
1.8 Hz); 3.83 (m, 1H, H-5); 2.05, 2.03, 2.01 (s, 9H, 3 ꢂ OCOCH3);
1.89 (s, 3H, NHCOCH3); 13C NMR (CDCl3, 125 MHz): d 171.3,
170.5, 170.3, 169.2 (COCH3); 163.9 (Cqv); 145.7 (Aryl-C); 142.3
(Cqv); 130.5, 125.3 (Aryl-C); 81.8 (C-1); 77.5 (C-5); 73.8 (C-4);
67.9 (C-3); 61.9 (C-6); 53.3 (C-2), 23.1 (NHCOCH3); 20.6, 20.5
(OCOCH3); 77Se NMR (CDCl3, 95.4 MHz): d 503. Anal. Calcd for
C19H23N3O10Se: C, 42.80; H, 4.32; N, 7.89. Found C, 43.51; H,
4.37; N, 7.87. HRMS m/z Calcd for: C19H23N3O10Se [M+Na]+:
556.050. Found: 556.047.
3.2.36. Phenyl 1-seleno-b-D-glucopyranoside (37)
From 36 (50 mg, 0.10 mmol), 27 mg (83%), syrup, ½a D22
ꢁ137 (c
ꢀ
0.4, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.70 (m, 2H, Aryl-H);
7.45–7.37 (m, 3H, Aryl-H); 4.80 (d, 1H, H-1, J1,2 9.4 Hz); 3.87 (dd,
1H, H-6a, J5,6a 4.9 Hz, J6a,6b 12.3 Hz); 3.65 (dd, 1H, H-6b, J5,6b
2.5 Hz); 3.40–3.23 (overlapping signals, 4H, H-2, H-3, H4, H-5);
13C NMR (CD3OD: 125 MHz): d 134.6 Aryl-C); 131.0 (Cqv.); 129.1
(Aryl-C); 127.9 (Aryl-C); 85.3 (C-1), 82.4 (C-5), 78.9 (C-3), 73.7
(C-4), 70.6 (C-2), 62.2 (C-6); 77Se NMR (CD3OD, 95.4 MHz): d 404.
HRMS m/z Calcd for C12H16O5Se [M+Na]+: 343.005. Found:
343.006.
3.2.37. 2,4-Dinitrophenyl 2,3,4,6,-tetra-O-acetyl-1-seleno-b-D-
glucopyranoside (38)38
3.2.41. 1-Se-Acetyl-2,3,4,6-tetra-O-acetyl-b-D-glucopyranose
From 3 (55 mg, 0.10 mmol), 2,4-dinitrophenyl bromide (5l,
(42)
22 mg, 0.11 mmol) and Et3N (15
l
L, 0.11 mmol), 38 mg (64%),
From 3 (55 mg, 0.10 mmol), acetic anhydride (5n, 26 lL,
white solid, mp 190–193 °C, lit.38 192–194 °C, ½a D22
ꢀ
ꢁ13 (c 1.6,
0.25 mmol) and Et3N (40 lL, 0.30 mmol), 26 mg (55%), syrup,
CHCl3), lit.38 ꢁ100 (c 5.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d
9.11 (s, 1H, Aryl-H); 8.38 (dd, 1H, Aryl-H); 8.03 (dd, 1H, Aryl-H);
5.34 (t, 1H, H-2); 5.27 (t, 1H, H-3, J3,4 9.0 Hz); 5.19 (t, 1H, H-4,
J4,5 8.5 Hz); 5.17 (d, 1H, H-1, J1,2 9.2 Hz); 4.27 (dd, 1H H-6a, J5,6a
5.6 Hz, J6a,6b 12.5 Hz); 4.21 (dd, 1H, H-6b, J5,6b 2.2 Hz); 3.91 (m,
1H, H-5); 2.12, 2.08, 2.06 (s, 12H, 4 ꢂ OCOCH3); 13C NMR (CDCl3,
125 MHz): d 169.9, 169.2 (COCH3); 145.9 (Cqv.); 140.4 (Cqv.);
131.1, 127.0, 121.3 (Aryl-C); 79.6 (C-1); 77.4 (C-5); 73.4 (C-2);
69.5 (C-3); 68.0 (C-4); 62.2 (C-6), 20.6, 20.5 (COCH3); 77Se NMR
(CDCl3, 95.4 MHz): d496. Anal. Calcd for C20H22N3O12Se: C, 41.50;
H, 3.80; N, 4.50. Found: C, 41.31; H, 3.81; N, 4.51. HRMS m/z Calcd
for C20H22N2O13Se [M+Na]+: 601.018. Found: 601.020.
½
a 2D2
ꢀ
ꢁ4 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz): d 5.28 (d, 1H,
H-1, J1,2 9.4 Hz); 5.23 (t, 1H, H-3); 5.19 (t, 1H, H-2); 5.12 (t, 1H,
H-4); 4.26 (dd, 1H, H-6a, J6a,6b 12.5 Hz, J5,6a 4.5 Hz); 4.11 (dd, 1H,
H-6b, J5,6b 2.0 Hz); 3.81 (m, 1H, H-5); 2.45 (s, 3H, SeCOCH3); 2.08,
2.03, 2.01, 2.00 (s, 12H, 4 ꢂ OCOCH3); 13C NMR (CDCl3,
125 MHz): d 194.3 (SeCOCH3); 170.5, 169.8, 169.2 (OCOCH3);
79.9 (C-1); 77.3 (C-5); 73.8 (C-3); 69.8 (C-2); 67.9 (C-4); 61.7 (C-
6); 34.7 (SeCOCH3); 20.6, 20.5, 20.4 (OCOCH3); 77Se NMR (CDCl3,
95.4 MHz): d 662. Anal. Calcd for: C16H22O10Se: C, 42.29; H, 4.84.
Found C, 42.43; H 4.06.
3.2.42. 1-Se-acetyl-2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-b-
D-
glucopyranose (43)
3.2.38. 2,4-Dinitrophenyl 1-seleno-b-
D
-glucopyranoside (39)
From 4 (100 mg, 0.21 mmol), acetic anhydride (5n, 52 lL,
From 38 (90 mg, 0.16 mmol), 55 mg (86%), syrup, ½a D22
ꢀ
ꢁ18 (c
0.50 mmol) and Et3N (53 lL, 0.40 mmol), 82 mg (89%), light pink
1.6, CD3OD); 1H NMR (CD3OD, 500 MHz): d 9.10 (s, 1H, Aryl-H);
8.42 (dd, 1H, Aryl-H); 8.25 (dd, 1H, Aryl-H); 5.24 (t, 1H, H-1, J2,3
10.0 Hz); 5.27 (t, 1H, H-3, J3,4 9.0 Hz); 5.19 (t, 1H, H-4, J4,5
8.5 Hz); 5.17 (d, 1H, H-1); 4.27 (dd, 1H, H-6a, J5,6a 5.6 Hz, J6a,6b
12.5 Hz); 4.21 (dd, 1H, H-6b, J5,6b 2.2 Hz); 3.91 (m, 1H, H-5); 13C
NMR (CDCl3, 125 MHz): d 155.8, 155.3, 148.9 (Cqv); 141.3, 137.3,
131.0 (Aryl-C); 87.5 (C-1); 85.4 (C-5); 82.4 (C-4); 79.1 (C-3); 77.5
(C-6); 71.6 (C-2); 77Se NMR (CD3OD, 95.4 MHz): d404. HRMS m/z
Calcd for C12H14N2O9Se [M+Na]+:432.975. Found: 432.978.
solid, mp 186–188 °C, ½a D22
ꢀ
ꢁ21 (c 1.6, CHCl3); 1H NMR (CDCl3,
500 MHz): d 5.60 (d, 1H, NH), 5.18 (overlapping signals H-1, H-
3); 5.08 (t, 1H, H-4); 4.48 (t, 1H, H-2); 4.26 (dd, H-6a, J5,6a 9.2 Hz,
J6a,6b 12.2 Hz); 4.11 (d, H-6b, J5,6b 3.0 Hz); 3.70 (m, 1H, H-5); 2.45
(s, 3H, SeCOCH3); 2.09, 2.05, 2.03 (s, 3H, 4x COCH3); 13C NMR
(CDCl3, 500 MHz): d 194.5 (SeCOCH3); 171.3, 170.6, 169.9, 169.2
COCH3); 81.6 (C-1); 77.5 (C-5); 74.1 (C-3); 67.7 (C-4); 61.8 (C-6);
53.2 (C-2); 34.7 (SeCOCH3); 23.1 (NHCOCH3); 20.7, 20.6, 20.5
(OCOCH3); 77Se NMR (CDCl3, 95.4 MHz): d 673. Anal. Calcd for
C16H23NO9Se: C, 42.48; H, 5.09; N, 3.10. Found: C, 42.95; H, 5.06;
3.2.39. (5-Nitropyrid-2-yl) 2,3,4,6-tetra-O-acetyl-1-seleno-b-
D
-
N, 3.13.
glucopyranoside (40)38
From 3 (100 mg, 0.19 mmol), 2-chloro-5-nitropyridine (5m,
3.2.43. 1-Se-Benzoyl-2,3,4,6-tetra-O-acetyl-b-D-glucopyranose
33 mg, 0.22 mmol) and Et3N (29
l
L, 0.22 mmol), 88 mg (88%), so-
(44)
lid, mp 178–179 °C, lit.38 176–178 °C, ½a D22
ꢀ
ꢁ26 (c 0.2, CHCl3),
From 3 (55 mg, 0.10 mmol), benzoyl chloride (5o, 15 mg,
lit.38 ꢁ4 (c 5.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d 9.29 (s, 1H,
Aryl-H); 8.27 (dd, 1H, Aryl-H); 7.50 (dd, 1H, Aryl-H); 5.90 (d, H-
1, J1,2 10.0 Hz); 5.51 (overlapping signals, 2H, H-4, H-3); 4.13 (m,
1H, H-4); 4.23 (dd, 1H, H-6a, J5,6a 2.0 Hz, J6a,6b 12.2 Hz); 4.10 (dd,
1H, H-6b, J5,6b 2.1 Hz); 3.75 (m, 1H, H-5); 2.20, 2.10, 2.05, 1.95 (s,
12H, 4x OCOCH3); 13C NMR (CDCl3, 125 MHz): d 170.3, 170.1,
0.20 mmol) and Et3N (27 lL, 0.11 mmol), 32 mg (60%), white solid,
mp 190–192 °C, ½a D22
ꢀ
ꢁ13 (c 0.1, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.84 (d, 1H, Aryl-H), 7.61 (t, 1H, Ar-H); 7.46 (t, 2H, Aryl-H); 5.53
(d, 1H, H-1, J1,2 10.3 Hz); 5.45-5.30 (overlapping signals 2H, H-2, H-
3); 5.18 (t, 1H, H-4, J3,4 10.1 Hz); 4.31 (dd, 1H, H-6a, J6a,6b 12.4 Hz,
J5,6a 4.6 Hz); 4.14 (dd, 1H, H-6b, J5,6b 2.1 Hz); 3.99 (m, 1H, H-5);