Xie et al.
FULL PAPER
DMSO-d6) δ: 160.2, 154.9, 135.0, 134.0, 125.7, 87.6,
87.2, 36.1, 31.2, 28.7-29.2, 26.4, 22.1, 13.9.
HRMS (ESI-TOF, positive) m/z calcd for C14H21N6O3
[M+H]+ 321.1670, found 321.1670.
Synthesis of 2-amino-6-decanylamino-9-(2',3'-dide-
oxy-β-D-glycero-pent-2-eno-furanosyl)purine (1l)
Synthesis of 2-amino-6-cyclopentylamino-9-(2',3'-di-
deoxy-β-D-glycero-pentfuranosyl)purine (2d)
To a suspension of 8 (211 mg, 0.788 mmol) in etha-
nol (10 mL) was added decanylamine (2 mL) and then
stirred at 100 ℃ autoclave for 2 h. The solvent was
removed and the residue was chromatographed by silica
gel decompression column with CH2Cl2/CH3OH (V∶V
=150∶1-80∶1) to give 1l as white solid (249 mg,
81%). UV (MeOH) λmax (ε): 224 (17178), 282 (11937)
Compound 2d can be prepared following the same
method for the preparation of 2a as described previously
from 1d. The reacting solution was stirred under H2 for
16 h to give a white foam with a yield of 85%. UV
(MeOH) λmax (ε): 224.5 (15644), 282.5 (10779) nm;
1
[α]2D0 −9.0 (c 0.13, MeOH); H NMR (500 MHz,
DMSO-d6) δ: 7.92 (s, 1H, 8-H), 7.07 (s, 1H, 6-NH),
6.01-6.03 (m, 1H, 1'-H), 5.77 (brs, 2H, 2-NH2), 5.05 (s,
1H, H-OH), 4.49 (brs, 1H, H-a), 4.04-4.08 (m, 1H,
4'-H), 3.57-3.62 (m, 1H, 5'-H1), 3.50-3.51 (m, 1H,
5'-H2), 2.26-2.37 (m, 2H, 2'-H), 1.99-2.06 (m, 2H,
3'-H), 1.89-1.90 (m, 2H, H-b1), 1.69-1.70 (m, 2H,
H-b2), 1.69-1.70 (m, 2H), 1.48-1.56 (m, 4H, H-c);
13C NMR (125 MHz, DMSO-d6) δ: 159.9, 154.5, 134.9,
83.6, 81.2, 63.0, 32.3, 31.6, 25.8, 23.4; HRMS
(ESI-TOF, positive) m/z calcd for C15H23N6O2 [M+H]+
319.1877, found 319.1879.
1
nm; [α]2D0 −9.7 (c 0.21, MeOH); H NMR (500 MHz,
DMSO-d6) δ: 7.71 (s, 1H, 8-H), 7.19 (brs, 1H, 6-H),
6.74-6.75 (m, 1H, 1'-H), 6.41-6.43 (m, 1H, 2'-H),
6.07-6.09 (m, 1H, 3'-H), 5.79 (brs, 2H, 2-NH2), 5.05 (t,
J=5.0 Hz, 1H, 5'-OH), 4.82-4.84 (m, 1H, 4'-H), 3.54
-3.56 (m, 2H, 5'-H), 1.53-1.55 (m, 2H, 6-H), 1.24-
1.28 (m, 16 H), 0.83-0.87 (m, 3H, CH3); 13C NMR
(125 MHz, DMSO-d6) δ: 160.2, 154.9, 135.0, 134.0,
125.7, 87.6, 87.2, 63.1, 31.3, 28.7-29.1, 26.4, 22.1,
13.9; HRMS (ESI-TOF, positive) m/z calcd for
C20H33N6O2 [M+H]+ 389.2659, found 389.2659.
Synthesis of 2-amino-6-cyclopropyamino-9-(2',3'-di-
deoxy-β-D-glycero-pentfuranosyl)purine (2f)
Synthesis of 2-amino-6-(1-piperidinyl)-9-(2',3'-dide-
oxy-β-D-glycero-pentfuranosyl)purine (2a)
Compound 2f can be prepared following the same
method for the preparation of 2a as described previously
from 1f. The reacting solution was stirred under H2 for
16 h to give white foam with a yield of 83%. UV
(MeOH) λmax (ε): 225 (16520), 282.5 (11950) nm;
To a solution of 1a (100 mg, 0.316 mmol) in THF
(1.5 mL) was added a small quantity of 10% Pd/C. The
mixture was stirred under H2 for 12 h. After filtering the
filtrate was evaporated and isolated by silica gel de-
compression column with CH2Cl2/CH3OH (V∶V=
100∶1) to give 2a as white foam (84 mg, 84%). UV
(MeOH) λmax (ε): 233.5 (14439), 287.5 (11665) nm;
1
[α]2D0 −11.9 (c 0.18, MeOH); H NMR (500 MHz,
DMSO-d6) δ: 7.92 (s, 1H, 8-H), 7.04 (s, 1H, 6-NH),
6.04-6.02 (m, 1H, 1'-H), 5.81 (s, 2H, 2-NH2), 5.02-
5.05 (t, J=5.0 Hz, 1H, 5'-OH), 4.04-4.08 (m, 1H,
4'-H), 3.47-3.62 (m, 2H, 5'-H), 3.02 (brs, 1H, H-a),
2.27-2.36 (m, 2H, 2'-H), 1.99-2.05 (m, 2H, 3'-H),
0.56 -0.67 (m, 6H, H-b); 13C NMR (125 MHz,
DMSO-d6) δ: 171.7, 159.9, 155.8, 137.1, 113.3, 83.6,
81.2, 63.0, 57.5, 31.6, 25.8, 22.1, 6.4, 5.6; HRMS
(ESI-TOF, positive) m/z calcd for C13H19N6O2 [M+H]+
291.1564, found 291.1565.
1
[α]2D0 −9.1 (c 0.15, MeOH); H NMR (500 MHz,
DMSO-d6) δ: 7.95 (s, 1H, 8-H), 6.04-6.06 (m, 1H,
1'-H), 5.81 (s, 2H, 2-NH2), 5.01 (s, 1H, H-OH), 4.04-
4.10 (m, >4H, H-a), 3.59-3.62 (m, 1H, 5'-H1), 3.49
-3.51 (m, 1H, 5'-H2), 2.24-2.38 (m, 2H, 2'-H), 1.98
-2.03 (m, 2H, 3'-H), 1.63-1.65 (m, 2H, H-c), 1.51-
1.55 (m, 4H, H-b); 13C NMR (125 MHz, DMSO-d6) δ:
159.5, 153.5, 152.4, 134.3, 113.5, 83.7, 81.4, 63.1, 31.7,
25.8, 24.4; HRMS (ESI-TOF, positive) m/z calcd for
C15H23N6O2 [M+H]+ 319.1877, found 319.1879.
Synthesis of 2-amino-6-dimethyamino-9-(2',3'-dide-
oxy-β-D-glycero-pentfuranosyl)purine (2g)
Synthesis of 2-amino-6-(1-morpholinyl)-9-(2',3'-dide-
To a solution of 1g (150 mg, 0.517mmol) in THF (2
mL) and EtOH (2 mL) was added a small quantity of
10% Pd/C. The mixture was stirred under H2 for 19 h.
After filtration, the filtrate was evaporated and isolated
twice by silica gel decompression column with
CH2Cl2/CH3OH (V∶V=100∶1) to give 2g as white
foam (89 mg, 59%). UV (MeOH) λmax (ε): 229.5
(16609), 284.5 (1720) nm; [α]2D0 −10.3 (c 0.13,
MeOH); 1H NMR (500 MHz, DMSO-d6) δ: 7.96 (s, 1H,
8-H), 6.04-6.06 (m, 1H, 1'-H), 5.80 (brs, 2H, 2-NH2),
5.01 (t, J=5.0 Hz, 1H, 5'-OH), 4.02-4.08 (m, 1H,
4'-H), 3.58-3.62 (m, 1H, 5'-H1), 3.48-3.52 (m, 1H,
5'-H2), 2.24-2.38 (m, 2H, 2'-H), 1.98-2.03 (m, 2H,
3'-H), 3.32 (s, 6H, CH3); 13C NMR (125 MHz,
DMSO-d6) δ: 159.3, 154.6, 152.1, 134.3, 113.8, 83.5,
oxy-β-D-glycero-pentfuranosyl)purine (2b)
Compound 2b can be prepared following the same
method for the preparation of 2a as described previously
from 1b. The reacting solution was stirred under H2 for
12 h to give white foam with a yield of 75%. UV
(MeOH) λmax (ε): 233 (16255), 288.5 (12217) nm;
1
[α]2D0 −9.6 (c 0.17, MeOH); H NMR (500 MHz,
DMSO-d6) δ: 7.99 (s, 1H, 8-H), 6.05-6.07 (m, 1H,
1'-H), 5.90 (brs, 2H, 2-NH2), 4.99 (t, J=5.0 Hz, 1H,
5'-OH), 4.04-4.10 (brs, >5H, H-a), 3.66-3.68 (m,
4H, H-b), 3.59-3.63, 3.48-3.52 (m, 1H, 1H, 5'-H),
2.24-2.39 (m, 2H, 2'-H), 1.98-2.02 (m, 2H, 3'-H); 13C
NMR (125 MHz, DMSO-d6) δ: 159.4, 153.6, 152.5,
134.7, 113.6, 83.6, 81.4, 66.2, 62.8, 44.9, 31.7, 25.6;
1214
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2013, 31, 1207—1218