S. S. Verma et al. / Carbohydrate Research 341 (2006) 1930–1937
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PyH), 7.79–7.72 (m, 1H, PyH), 7.41–7.15 (m, 6H, PyH,
ArH), 6.08, 5.97 (each d, J 3.3 and 2.7 Hz, 1H, H-1),
5.01 (m, 1H, H-7), 4.64–4.57 (m, 1H, H-5), 4.47–4.37
(m, 2H, OCH2Ph), 4.23–4.01 (m, 4H, H-2, OCH2, H-
3), 3.89–3.68 (m, 1H, H-6), 2.05 (br s, 1H, OH), 1.39,
1.37 (s, 6H, CMe2), 1.20 (t, J 8.7 Hz, 3H, Me); 13C
NMR (50 MHz, CDCl3): d 173.5, 173.1 (C@O), 156.0,
155.0 (C-4), 149.5, 148.9, 137.5, 137.4, 135.0, (PyC),
128.9, 128.2, 128.1, 123.7, 123.4 (ArC), 114.4, 114.3
(CMe2), 107.3 (C-1), 98.9, 98.4 (C-5), 83.4, 80.7 (C-2,
C-3), 73.7 (C-7), 70.5, 70.1 (OCH2Ph), 61.5 (OCH2),
50.3, 50.1 (C-6), 28.2, 27.9, 27.7, 27.3 (CMe2), 14.4
(Me); FABMS: m/z = 456 [M+H]+. Anal. Calcd for
C25H29O7N: C, 65.93; H, 6.15; N, 3.07. Found: C,
65.80; H, 6.10; N, 3.10.
(OCH2Ph), 61.2 (OCH2Me), 56.1, 55.9 (OMe), 50.5,
50.1 (C-6), 28.2, 27.3 (CMe2), 14.5 (Me); FABMS:
m/z = 515 [M+H]+. Anal. Calcd for C28H34O9: C,
65.36; H, 6.61. Found: C, 65.30; H, 6.60.
1.7. (4Z) 3-O-Benzyl-6-carbethoxy-5,6-dideoxy-7-
hydroxy-1,2-O-isopropylidene-7-(thiophene-2-yl)-
b-L-threo-hept-4-enofuranose (3d)
From 2a (1.0 g, 2.87 mmol) as a colourless viscous syrup
27
(1.03 g, 78%); ½aꢁD ꢀ25 (c 0.10, CHCl3); IR (neat): 3470,
1
1722 cmꢀ1; H NMR (200 MHz, CDCl3): d 7.36–7.17
(m, 5H, ArH), 7.03 (d, J 3.2 Hz, 1H, ThiophH), 6.96–
6.88 (m, 2H, ThiophH), 6.08, 6.06 (each d, J 3.0 Hz,
1H, H-1), 5.23–5.16 (m, 1H, H-7), 4.72–4.59 (m, 1H,
H-5), 4.40, 4.25 (d, J 12.4 Hz, 2H, PhCH2), 4.16 (d, J
3.0 Hz, 1H, H-2), 4.13 (q, J 7.2, 2H, OCH2Me), 4.00
(s, 1H, H-3), 3.69 (m, 1H, H-6), 2.06 (br s, 1H, OH),
1.39, 1.35 (s, 6H, CMe2), 1.22 (t, J 7.2 Hz, 3H, Me);
13C NMR (50 MHz, CDCl3): d 173.2 (C@O), 154.7
(C-4), 137.5, 128.8, 128.7, 128.2, 128.1, 126.9, 125.4,
125.1, 124.9, 124.6 (Ar–C, ThiophC), 114.3 (CMe2),
107.4 (C-1), 99.4 (C-5), 83.5, 80.6 (C-2, C-3), 71.8 (C-
7), 70.3 (OCH2Ph), 61.3 (OCH2Me), 50.3, (C-6), 28.3,
27.6 (CMe2), 14.5 (Me); FABMS: m/z = 461 [M+H]+.
Anal. Calcd for C24H28O7S: C, 62.60; H, 6.08. Found:
C, 62.61; H, 6.03.
1.5. (4Z) 3-O-Benzyl-6-carbethoxy-5,6-dideoxy-7-
hydroxy-1,2-O-isopropylidene-7-(2-pyridyl)-b-L-
threo-hept-4-enofuranose (3b)
From 2a (1.0 g, 2.87 mmol) as a colourless viscous syrup
27
(1.05 g, 82%); ½aꢁD ꢀ40 (c 0.10, CHCl3); IR (neat): 3449,
1
1722 cmꢀ1; H NMR (200 MHz, CDCl3): d 8.53–8.42
(m, 1H, PyH), 7.67–7.17 (m, 8H, PyH, ArH), 5.94,
5.84 (each d, J 3.0 and 2.8 Hz, 1H, H-1), 5.28–5.00 (m,
1H, H-7), 4.84–4.60 (m, 1H, H-5), 4.50–4.24 (m, 2H,
PhCH2), 4.21–4.04 (m, 4H, H-2, OCH2, H-3), 3.70–
3.65 (m, 1H, H-6), 2.26 (br s, 1H, OH), 1.37 and 1.32
(each s, each 3H, CMe2), 1.13 (t, J = 6.8 Hz, 3H, Me);
13C NMR (50 MHz, CDCl3): d 172.8 (C@O), 154.6,
154.1 (C-4), 148.7, 148.1, 137.6, 136.9 (PyC), 128.8,
128.2 (ArC), 123.0, 121.8, (ArC, PyC), 114.3 (CMe2),
107.3, 107.0 (C-1), 99.7, 98.1 (C-5), 83.5, 80.6 (C-2, C-
3), 73.4 (C-7), 70.4 (OCH2Ph), 61.4, 61.1 (OCH2Me),
50.2, 49.3 (C-6), 28.2, 27.6 (CMe2), 14.5 (Me); FABMS:
m/z = 456 [M+H]+. Anal. Calcd for C25H29O7N: C,
65.93; H, 6.15; N, 3.07. Found: C, 65.90; H, 6.12; N,
3.11.
1.8. (4Z) 3-O-Benzyl-6-carbethoxy-5,6-dideoxy-7-
hydroxy-1,2-O-isopropylidene-7-phenyl-b-L-threo-
hept-4-enofuranose (3e)
From 2a (1.0 g, 2.87 mmol) as a colourless viscous syrup
27
(1.10 g, 85%); ½aꢁD ꢀ16 (c 0.10, CHCl3); IR (neat): 3470,
1
1722 cmꢀ1; H NMR (200 MHz, CDCl3): d 7.41–7.11
(m, 10H, ArH), 6.09, 6.00 (each d, J 3.2, 2.8 Hz, 1H,
H-1), 5.22–5.16 (m, 1H, H-7), 4.99–4.67 (m, 1H, H-5),
4.69 (m, 2H, PhCH2), 4.40 (d, J 3.0 Hz, 1H, H-2), 4.19
(m, 2H, OCH2Me), 4.00 (s, 1H, H-3), 3.71, 3.69 (m,
1H, H-6), 2.06 (br s, 1H, OH), 1.41, 1.39 and 1.35,1.30
(s, 6H, CMe2), 1.19 (t, J 7.0 Hz, 3H, Me); FABMS:
m/z = 455 [M+H]+. Anal. Calcd for C26H3O7: C,
68.72; H, 6.60. Found: C, 68.69; H, 6.78.
1.6. (4Z) 3-O-Benzyl-6-carbethoxy-5,6-dideoxy-7-
hydroxy-1,2-O-isopropylidene-7-(3,4-dimethoxyphenyl)-
b-L-threo-hept-4-enofuranose (3c)
From 2a (1.0 g, 2.87 mmol) as a colourless viscous syrup
27
(1.21 g, 83%); ½aꢁD ꢀ37 (c 0.10, CHCl3); IR (neat): 3469,
1.9. (4Z) 6-Carbethoxy-5,6-dideoxy-7-hydroxy-1,2-O-
isopropylidene-3-O-methyl-7-(3-pyridyl)-b-L-threo-hept-
4-enofuranose (3f)
1725 cmꢀ1; H NMR (200 MHz, CDCl3): d 7.36–7.26
1
(m, 5H, ArH), 7.11–7.01 (m, 3H, ArH), 6.07, 5.99 (each
d, J 3.4 Hz, 1H, H-1), 4.96–4.89 (m, 1H, H-7), 4.69–4.50
(m, 1H, H-5), 4.50–4.40 (m, 3H, PhCH2, H-2), 4.20 (q, J
7.2 Hz, 2H, OCH2), 4.09 (s, 1H, H-3), 3.86, 3.71 (s, 3H,
OMe), 3.90 (m, 1H, H-6), 2.06 (br s, 1H, –OH), 1.41,
1.39 (s, 6H, CMe2), 1.19 (t, J 7.2 Hz, 3H, OCH2Me);
13C NMR (50 MHz, CDCl3): d 173.7, 173.5 (C@O),
154.5, 154.1 (C-4), 137.4, 134.3, 128.8, 128.7, 128.2,
128.1, 120.0, 119.4 (ArC), 114.3 (CMe2), 107.3 (C-1),
98.3 (C-5), 83.5, 80.7 (C-2, C-3), 75.3 (C-7), 70.2
From 2b (1.0 g, 2.87 mmol) as a colourless viscous syrup
27
(1.20 g, 87%); ½aꢁD ꢀ60 (c 0.10, CHCl3); IR (neat): 3469,
1
1729 cmꢀ1; H NMR (200 MHz, CDCl3): d 8.59–8.46
(m, 2H, PyH), 7.72 (d, J 8.0 Hz, PyH), 7.30–7.20 (m,
1H, PyH), 6.01, 5.89 (each d, J 3.0 and 2.8 Hz, 1H, H-
1), 5.30–5.19 (m, 1H, H-7), 4.82–4.60 (m, 1H, H-5),
4.46–4.39 (m, 1H, H-2), 4.16–4.09 (m, 2H, OCH2Me),
3.94, 3.92 (each s, each 1H, H-3), 3.70–3.65 (m, 1H,