B. Liberek et al. / Carbohydrate Research 337 (2002) 1803–1810
1809
Ethyl 3-acetamido-4,6-di-O-acetyl-2,3-dideoxy-h-D-
Methyl
3-acetamido-2,3-dideoxy-h-D-arabino-
arabino-hexopyranoside (35).—Reduction of 3-azido
group in 17 followed by acetylation resulted in 35 (67%,
syrup); [h]D+97° (c 0.5, CHCl3), Rf 0.50 (solvent A);
IR: w 3220 (NH), 1745 and 1250 (ester), 1670 and 1550
hexopyranoside (31).—Acetylation of 30 resulted in 31
(73%); mp 134–136 °C (EtOH−n-hexane); [h]D+132°
(c 0.7, CHCl3); Rf 0.47 (solvent G); IR: w 3296 (OH,
NH), 1640 and 1555 (amide) cm−1 1H NMR (500
;
1
(amide) cm−1; H NMR (100 MHz, CD3Cl): l 1.23 (t,
MHz, CD3Cl): l 1.66 (td, 1 H, J2a,2e=J2a,3 12.5 Hz,
H-2a), 2.02 (s, 3 H, AcNH), 2.04 (dq, 1 H, J2e,3 4.8 Hz,
H-2e), 3.38 (t, 1 H, J4,5 9.8 Hz, H-4), 3.42 (s, 3 H,
OCH3), 3.59 (m, 1H, J5,6 7.5, J5,6% 2.8 Hz, H-5), 3.75
(dd, 1 H, J6,6% 12.0 Hz, H-6), 3.90 (dd, 1 H, H-6%), 4.23
(dq, 1 H, J3,4 9.8 Hz, H-3), 4.83 (d, 1 H, J1,2a 3.0 Hz,
H-1). Anal. Calcd for C9H17NO5: C, 49.31; H, 7.82; N,
6.39. Found: C, 47.35; H, 7.88; N, 5.91.
3 H, CH2CH3), 1.65 (td, 1 H, J2a,2e=J2a,3 13.5 Hz,
H-2a), 1.94 (s, 3 H, AcNH), 2.09, 2.11 (2 s, 6 H, 2
OAc), 2.25 (dd, 1 H, J2e,3 4 Hz, H-2e), 3.63 (q, 2 H,
CH2CH3), 4.07 (m, 2 H, J5,6 5, J5,6% 2 Hz, H-5, H-6%),
4.40 (dd, 1 H, J6,6% 13 Hz, H-6), 4.60 (m, 1 H, J3,4 10
Hz, H-3), 4.80 (t, 1 H, J4,5 10 Hz, H-4), 4.97 (d, 1 H,
J1,2a 3.5 Hz, H-1), 5.67 (bd, 1 H, J3,NH 8 Hz, NH).
FDMS: m/z 317 (M+). Anal. Calcd for C14H23NO7: C,
52.99; H, 7.31; N, 4.41. Found: C, 53.12; H, 7.15; N,
4.20.
Methyl
3-amino-2,3-dideoxy-i-D-arabino-hexopy-
ranoside (32).—Reduction of 3-azido group in 11
yielded 32 (84%, syrup); [h]D−51° (c 0.7, CH3OH),
lit.2−62°; Rf 0.29 (solvent F); IR: w 3348 (OH, NH2),
Ethyl 3-acetamido-4,6-di-O-acetyl-2,3-dideoxy-i-D-
ribo-hexopyranoside (36).—Reduction of 3-azido group
in 18 followed by acetylation yielded 36 (57%, syrup);
[h]D−79° (c 0.4, CHCl3); Rf 0.60 (solvent A); IR: w
3200 (NH), 1740 and 1240 (ester), 1660 and 1545
1591 (NH) cm−1 1H NMR (500 MHz, CD3OD): l
;
1.40 (td, 1 H, J2a,2e 12.7, J2a,3 12.2 Hz, H-2a), 2.06 (dq,
1 H, J2e,3 4.4 Hz, H-2e), 2.78 (dq, 1 H, J3,4 9.3 Hz, H-3),
3.09 (t, 1 H, J4,5 9.3 Hz, H-4), 3.25 (dq, 1H, J5,6 5.9, J5,6%
2.4 Hz, H-5), 3.50 (s, 3 H, OCH3), 3.71 (dd, 1 H, J6,6%
12.21 Hz, H-6), 3.89 (dd, 1 H, H-6%), 4.51 (dd, 1 H, J1,2a
9.3, J1,2e 1.9 Hz, H-1); 13C NMR (500, CD3OD): l
37.70 (C-2), 52.46 (C-6), 55.30 (OCH3), 61.43 (C-3),
71.74 (C-5), 77.64 (C-4), 101.18 (C-1).
1
(amide) cm−1; H NMR (100 MHz, CD3Cl): l 1.21 (t,
3 H, CH2CH3), 1.75–2.20 (m, 2 H, 2 H-2), 2.03 (s, 3 H,
AcNH), 2.13 (s, 6 H, 2 AcO), 3.57 (q, 2 H, CH2CH3),
3.80–4.15 (m, 2 H, H-5, H-6%), 4.35 (dd, 1 H, H-6), 4.70
(m, 1 H, J3,4=J2a,3=J2e,3 4 Hz, H-3), 4.86 (t, 1 H,
J4,5=J3,4 4 Hz, H-4), 5.03 (t, 1 H, J1,2a=J1,2e 4 Hz,
Methyl
3-acetamido-2,3-dideoxy-i-D-arabino-
H-1), 5.64 (bd, 1 H, J3,NH 8 Hz, NH). FDMS: m/z 317
(M+). Anal. Calcd for C14H23NO7: C, 52.99; H, 7.31;
N, 4.41. Found: C, 53.08; H, 6.99; N, 4.11.
hexopyranoside (33).—Acetylation of 32 gave 33 (75%);
mp 174–176 °C (EtOH−n-hexane); [h]D−17° (c 0.5,
CHCl3); Rf 0.49 (solvent G); IR: w 3273 (OH, NH),
Ethyl 3-acetamido-4,6-di-O-acetyl-2,3-dideoxy-i-D-
1640 and 1553 (amide) cm−1 1H NMR (500 MHz,
;
arabino-hexopyranoside (37).—Reduction of 3-azido
group in 19 followed by acetylation resulted in 37 (67%,
syrup); [h]D−12° (c 0.9, CHCl3); Rf 0.40 (solvent A);
IR: w 3200 (NH), 1740 and 1250 (ester), 1660 and 1550
CD3Cl): l 1.24 (td, 1 H, J2a,2e=J2a,3 12.5 Hz, H-2a),
1.79 (s, 3 H, AcNH), 1.87 (dq, 1 H, J2e,3 4.5 Hz, H-2e),
3.08 (t, 1 H, J4,5 9.4 Hz, H-4), 3.11 (m, 1H, J5,6 4.9, J5,6%
1.8 Hz, H-5), 3.31 (s, 3 H, OCH3), 3.53 (dd, 1 H, J6,6%
11.6 Hz, H-6), 3.70 (dd, 1 H, H-6%), 3.72 (m, 1 H, J3,4
9.4 Hz, H-3), 4.32 (dd, 1 H, J1,2a 9.8, J1,2e 1.8 Hz, H-1);
13C NMR (500 MHz, CD3Cl): l 22.90 (COCH3), 38.17
(C-2), 52.74 (C-6), 56.96 (OCH3), 62.93 (C-3), 70.72
(C-5), 79.40 (C-4), 102.50 (C-1), 173.57 (CꢀO). Anal.
Calcd for C9H17NO5: C, 49.31; H, 7.82; N, 6.39.
Found: C, 49.27; H, 7.86; N, 6.17.
1
(amide) cm−1; H NMR (100 MHz, CD3Cl): l 1.24 (t,
3 H, CH2CH3), 1.64 (td, 1 H, J2a,2e=J2a,3 13.5 Hz,
H-2a), 1.96 (s, 3 H, AcNH), 2.10 (s, 6 H, 2 OAc), 2.30
(dq, 1 H, J2e,3 5 Hz, H-2e), 3.60 (q, 2 H, CH2CH3), 3.70
(dq, 1 H, J5,6 5, J5,6% 2.5 Hz, H-5), 4.15 (dd, 1 H, H-6%),
4.35 (m, 1 H, J3,4 10 Hz, H-3), 4.40 (dd, 1 H, J6,6% 12.5
Hz, H-6), 4.65 (dd, 1 H, J1,2a 10, J1,2e 2 Hz, H-1), 4.80
(t, 1 H, J4,5 10 Hz, H-4), 6.10 (bd, 1 H, J3,NH 8 Hz,
NH). FDMS: m/z 317 (M+). Anal. Calcd for
C14H23NO7: C, 52.99; H, 7.31; N, 4.41. Found: C,
52.18; H, 7.10; N, 4.24.
Methyl
3-amino-2,3-dideoxy-h-D-ribo-hexopyran-
oside (34).—Reduction of 3-azido group in 12 yielded
34 (78%, syrup); [h]D+71° (c 0.6, CH3OH); Rf 0.22
(solvent F); IR: w 3335 (OH, NH2), 1604 (NH) cm−1
;
Ethyl 3-acetamido-4,6-di-O-acetyl-2,3-dideoxy-h-D-
1H NMR (500 MHz, CD3OD): l 1.70 (dq, 1 H, J2a,2e
14.6, J2a,3 3.9 Hz, H-2a), 2.40 (dd, 1 H, J2e,3 1.96 Hz,
H-2e), 2.62 (bs, 1 H, OH), 3.02 (dd, 1 H, J6,6% 12.21 Hz,
H-6), 3.36 (m, 1 H, J3,4 2.93 Hz, H-3), 3.41 (m, 1 H,
H-6%), 3.46 (s, 3 H, OCH3), 4.02 (m, 1H, J5,6 5.86, J5,6%
3.42 Hz, H-5), 4.03 (dd, 1 H, J4,5 9.28 Hz, H-4), 4.77 (d,
1 H, J1,2a 5.86, H-1); 13C NMR (500, CD3OD): l 32.12
(C-2), 46.54 (C-6), 52.96 (C-3), 55.58 (OCH3), 69.71
(C-5), 74.73 (C-4), 97.89 (C-1).
ribo-hexopyranoside (38).—Reduction of 3-azido group
in 20 followed by acetylation gave 38 (48%, syrup);
[h]D+45° (c 0.8, CHCl3); Rf 0.27 (solvent A); IR: w
3300 (NH), 1735 and 1240 (ester), 1670 and 1520
1
(amide) cm−1; H NMR (100 MHz, CD3Cl): l 1.28 (t,
3 H, CH2CH3), 1.70–2.25 (m, 2 H, 2 H-2), 2.00 (s, 6 H,
2 OAc), 2.10 (s, 3 H, AcNH), 3.60 (q, 2 H, CH2CH3),
4.05–4.30 (m, 3 H, H-5, 2 H-6), 4.73 (m, 1 H, J3,4
=
J2a,3=J2e,3 4 Hz, H-3), 4.90 (dd, 1 H, J4,5 10 Hz, H-4),