requires C 64.05, H 8.05, N 4.15%); νmax/cmϪ1 (KBr) 3374 (OH),
3040 (CH aromatic), 2971, 2932, 2874 (CH aliphatic), 1459
(CC aromatic); δH(400 MHz, CDCl3) 7.53–7.51 (2H, m, Ph),
7.38–7.31 (3H, m, Ph), 5.58 (1H, s, CHPh), 4.54 (1H, d, J 8.5,
H-1), 4.33 (1H, dd, J 10.4 and 5.0, H-6), 3.83 (1H, pt, J 10.3,
H-6Ј), 3.69 (1H, pt, J 9.4, H-3), 3.63 (1H, pt, J 9.0, H-4), 3.52
(3H, s, OCH3), 3.42 (1H, ddd, J 10.6, 9.1 and 5.0, H-5), 2.81
(2H, dq, J 13.0 and 7.3, NCH2), 2.71 (2H, dq, J 13.0 and 6.9,
NCH2), 2.63 (1H, pt, J 9.1, H-2), 1.08 (6H, t, J 7.1, CH2CH3);
δC(100 MHz, CDCl3) 137.2, 129.0, 128.2, 126.3 (Ph), 103.4
(C-1), 101.5 (CHPh), 81.8 (C-4), 68.8 (C-6), 68.2 (C-3), 66.6
(C-5), 65.8 (C-2), 56.7 (OCH3), 44.5 (CH2CH3), 14.8 (CH2-
CH3); m/z (TOF, ESϩ) 338.1966 ([M ϩ H]ϩ, C18H28NO5
requires 338.1967).
for 12 h, then at 78 ЊC for 8 h. A further portion of 1,5-diiodo-
pentane (53 µl) was then added and the reaction was heated
at reflux for 15 h. Purification by column chromatography
(2.5–15% MeOH–DCM) afforded 4h (210 mg, 85%) as an
amorphous, white solid; Rf 0.4 (10% MeOH–EtOAc); [α]2D4
ϩ106 (c 1.63, CHCl3) (Found: C 65.0, H 7.7, N 4.0. C19H27NO5
requires C 65.3, H 7.8, N 4.0%); νmax/cmϪ1 (KBr) 3454br (OH),
2929, 2852 (CH, aliphatic), 1455 (CC, aromatic); δH(400 MHz,
CDCl3) 7.53–7.51 (2H, m, Ph), 7.38–7.33 (3H, m, Ph), 5.58 (1H,
s, CHPh), 4.85 (1H, d, J 3.0, H-1), 4.26 (1H, dd, J 9.6 and 4.3,
H-6), 4.13 (1H, dd, J 10.6 and 8.8, H-3), 3.84 (1H, ddd, J 10.3,
9.1 and 4.4, H-5), 3.77 (1H, pt, J 10.0, H-6Ј), 3.59 (1H, pt, J 9.0,
H-4), 3.39 (3H, s, OCH3), 2.83–2.78 (2H, m, NCH2), 2.67 (1H,
dd, J 10.6 and 3.0, H-2), 2.67–2.63 (2H, m, NCH2), 1.63–1.46
(6H, m, NCH2CH2, NCH2CH2CH2); δC(100 MHz, CDCl3)
137.3, 129.0, 128.1, 126.4 (Ph), 101.7 (CHPh), 98.8 (C-1), 83.4
(C-4), 69.4 (C-2), 69.1 (C-6), 64.8 (C-3), 62.3 (C-5), 54.6
(OCH3), 51.0 (NCH2), 27.0 (NCH2CH2), 24.7 (NCH2CH2-
CH2); m/z (TOF, ESϩ) 350.1971 ([M ϩ H]ϩ, C19H28NO5
requires 350.1967).
Methyl 4,6-O-benzylidine-2-deoxy-2-N-n-propylamino-ꢀ-D-
glucopyranoside 4d
1.1 Equivalents of propyl iodide (76 µL) and potassium
carbonate (108 mg) were used; the reaction was heated at reflux
for a total of 48 h, a further portion of propyl iodide (14 µL)
was added after 28 h. Purification by column chromatography
(5% MeOH–CHCl3) afforded 4d as a white solid (144 mg, 63%);
Rf 0.5 (5% MeOH–CHCl3); mp 89.5–91 ЊC (DCM); [α]2D4 ϩ102
(c 1.13, CHCl3); (Found: C 62.8, H 7.9, N 4.3. C17H25NO5
requires C 63.15, H 7.8, N 4.35%); νmax/cmϪ1 (KBr) 3319, 3296
(OH, NH), 3061, 3038, (CH, aromatic), 2997, 2975, 296, 2922,
2906, 2866, 2832 (CH, aliphatic), 1470, 1431 (CC, aromatic);
δH(400 MHz, CDCl3) 7.52–7.50 (2H, m, Ph), 7.39–7.33 (3H, m,
Ph), 5.57 (1H, s, CHPh), 4.84 (1H, d, J 3.5, H-1), 4.28 (1H, m,
H-6), 3.83–3.74 (2H, m, H-5, H-6Ј), 3.73 (1H, pt, J 9.5, H-3),
3.57 (1H, pt, J 9.1, H-4), 3.42 (3H, s, OCH3), 2.74 (1H, ddd, J
11.2, 8.0 and 6.4, NHCH2), 2.63 (1H, dd, J 9.9 and 3.5, H-2),
2.50 (1H, ddd, J 11.2, 8.2 and 6.2, NHCH2), 1.58–1.43 (2H, m,
CH2CH3), 0.93 (3H, t, J 7.3, CH2CH3); δC(100 MHz, CDCl3)
137.2, 129.1, 128.2, 126.4 (4 × Ph), 101.8 (CHPh), 98.3 (C-1),
82.0 (C-4), 69.4 (C-3), 69.1 (C-6), 63.2 (C-2), 62.3 (C-5), 55.4
(OCH3), 49.5 (NHCH2), 23.7 (CH2CH3), 11.6 (CH2CH3);
m/z (TOF, ESϩ) 338.1805 ([M ϩ H]ϩ, C17H26NO5 requires
324.1811).
Methyl 4,6-O-benzylidine-2-deoxy-2-(1-piperidinyl)-ꢁ-D-gluco-
pyranoside 5h
1.1 Equivalents of 1,5-diiodopentane (116 µL) and potassium
carbonate 108 mg) were used; the reaction was heated at 60 ЊC
for 12 h, then at 78 ЊC for 8 h. A further portion of 1,5-diiodo-
pentane (53 µL) was then added and the reaction was heated
at reflux for 15 h. Purification by column chromatography (0–
10% MeOH–DCM) afforded 5h (223 mg, 90%) as an amorph-
ous, light yellow solid; Rf 0.7 (10% MeOH–EtOAc); [α]2D4 Ϫ22
(c 1.03, CHCl3); νmax/cmϪ1 (KBr) 3440br (OH), 2932, 2825 (CH,
aliphatic), 1469, 1454 (CC, aromatic); δH(400 MHz, CDCl3)
7.53–7.50 (2H, m, Ph), 7.37–7.33 (3H, m, Ph), 5.71 (1H, s,
CHPh), 4.53 (1H, d, J 8.6, H-1), 4.32 (1H, dd, J 10.4 and 5.1,
H-6), 3.82 (1H, pt, J 10.4, H-6Ј), 3.74 (1H, pt, J 9.5, H-3), 3.60
(1H, pt, J 9.1, H-4), 3.55 (3H, s, OCH3), 3.40 (1H, ddd, J 10.0,
9.3 and 5.0, H-5), 3.02–2.97 (2H, m, NCH2), 2.55–2.51 (2H, m,
NCH2), 2.39 (1H, dd, J 9.9 and 8.6, H-2), 1.60–1.47 (6H, m,
NCH2CH2, NCH2CH2CH2); δC(100 MHz, CDCl3) 137.2, 129.0,
128.2, 126.4 (4 × Ph), 102.8 (C-1), 101.5 (CHPh), 81.7 (C-4),
70.8 (C-2), 68.8 (C-6), 67.8 (C-3), 66.7 (C-5), 56.5 (OCH3),
51.2 (br, NCH2), 27.0 (NCH2CH2), 24.6 (NCH2CH2CH2);
m/z (TOF, ESϩ) 350.1967 ([M ϩ H]ϩ, C19H28NO5 requires
350.1967).
Methyl 4,6-O-benzylidine-2-deoxy-2-N,N-di-n-propylamino-
ꢀ-D-glucopyranoside 4e
3 Equivalents of propyl iodide (208 µL) and 2.1 equivalents
of potassium carbonate (206 mg) were used; the reaction was
heated at reflux for a total of 48 h, a further portion of propyl
iodide (138 µL) was added after 28 h. Purification by column
chromatography (2% MeOH–CHCl3) afforded 4e as a colour-
less syrup (186 mg, 72%); Rf 0.6 (5% MeOH–CHCl3); [α]2D4 ϩ123
(c 1.84, CHCl3); (Found: C 65.3, H 8.6, N 3.8. C20H31NO5
requires C 65.75, H 8.55, N 3.85%); νmax/cmϪ1 (CHCl3) 3438
(OH), 2936, 2933, 2874, 2842 (CH, aliphatic), 1470, 1458 (CC,
aromatic); δH(400 MHz, CDCl3) 7.53–7.51 (2H, m, Ph), 7.38–
7.31 (3H, m, Ph), 5.59 (1H, s, CHPh), 4.83 (1H, d, J 3.0, H-1),
4.27 (1H, dd, J 9.9 and 4.5, H-6), 4.09 (1H, dd, J 10.5 and 8.7,
H-3), 3.85 (1H, ptd, J 9.9 and 4.5, H-5), 3.77 (1H, pt, J 10.1,
H-6Ј), 3.61 (1H, pt, J 9.0, H-4), 3.38 (3H, s, OCH3), 2.81 (1H,
dd, J 10.5 and 3.2, H-2), 2.74 (2H, ddd, J 13.5, 9.0 and 7.2,
NCH2), 2.53 (2H, ddd, J 13.5, 8.7 and 4.7, NCH2), 1.55–1.34
(4H, m, CH3CH2), 0.88 (6H, t, J 7.3, CH2CH3); δC(100 MHz,
CDCl3) 137.3, 129.0, 128.2, 126.4 (4 × Ph), 101.7, (CHPh), 99.1
(C-1), 83.3 (C-4), 69.2 (C-6), 65.6 (C-3), 65.0 (C-2), 62.2 (C-5),
54.8 (OCH3), 52.7 (NCH2), 22.3 (CH2CH3), 11.6 (CH2CH3);
m/z (TOF, ESϩ) 366.2287 ([M ϩ H]ϩ, C20H32NO5 requires
366.2280).
Methyl 4,6-O-benzylidine-2-deoxy-2-(4-morpholinyl)-ꢀ-D-gluco-
pyranoside 4i
1.1 Equivalents of di(2-iodoethyl)ether35 (255 mg) and potas-
sium carbonate (108 mg) were used; the reaction was heated at
70 ЊC for 24 h a further portion of di(2-iodoethyl)ether (70 mg)
was then added and the reaction was heated at reflux for 6 h.
Purification by column chromatography (2.5–5% MeOH–
DCM) afforded 4i (226 mg, 0.64 mmol, 91%) as a white solid;
Rf 0.4 (5% MeOH–CHCl3); mp 155–157.5 ЊC (DCM); [α]2D4 ϩ92
(c 1.97, CHCl3); (Found: C 61.5, H 7.2, N 4.0. C18H25NO6
requires C 61.5, H 7.15, N 4.0%); νmax/cmϪ1 (KBr) 3440 (OH),
3067w (CH, aromatic), 2975, 2928, 2863 (CH, aliphatic), 1458
(CC, aromatic); δH(400 MHz, CDCl3) 7.52–7.49 (2H, m, Ph),
7.39–7.34 (3H, m, Ph), 5.57 (1H, s, CHPh), 4.85 (1H, d, J 3.1,
H-1), 4.27 (1H, dd, J 9.6 and 4.2, H-6), 4.18 (1H, dd, J 10.3 and
9.1, H-3), 3.83 (1H, ddd, J 10.3, 9.0 and 4.3, H-5), 3.76 (1H, pt,
J 9.6, H-6Ј), 3.71 (2H, ddd, J 11.1, 5.7 and 3.4, CH2O), 3.66
(2H, ddd, J 11.1, 5.7 and 3.4, CH2O), 3.57 (1H, pt, J 9.1, H-4),
3.40 (3H, s, OCH3), 3.15 (1H, s, OH), 2.84 (4H, m, CH2N),
2.70 (1H, dd, J 10.6 and 3.1, H-2); δC(100 MHz, CDCl3) 137.2,
129.1, 128.2, 126.3 (4 × Ph), 101.8 (PhCH), 99.3 (C-1), 83.2
(C-4), 69.1 (C-6), 68.6 (C-2), 67.8 (CH2O), 65.4 (C-3), 62.2
(C-5), 54.7 (OCH3), 50.3 (CH2N); m/z (TOF, ESϩ) 352.1772
([M ϩ H]ϩ, C18H26NO6 requires 352.1760).
Methyl 4,6-O-benzylidine-2-deoxy-2-(1-piperidinyl)-ꢀ-D-gluco-
pyranoside 4h
1.1 Equivalents of 1,5-diiodopentane (116 µL) and potassium
carbonate (108 mg) were used; the reaction was heated at 60 ЊC
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 8 2 6 – 3 8 3 8
3832