The Journal of Organic Chemistry
Page 24 of 41
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(
m, 12 H), 3.80-3.68 (m, 5 H), 3.59-3.47 (m, 5 H), 2.26 (s, 1.5 H, Ac), 2.25 (s, 1.5 H, Ac), 2.10
13
(
s, 1.5 H, Ac, Ph-CH
): δ 170.1, 170.0, 169.9, 138.5 (2C), 138.4 (2C), 138.2 (2C), 138.1 (2C), 138.0 (2C), 137.9
2C), 137.8 (2C), 137.6 (4C), 137.5, 137.4, 132.4, 131.5, 130.7, 130.4, 129.8, 129.7, 128.4 (3C),
3 3
), 2.08 (s, 3 H, Ac, Ph-CH ), 1.95 (s, 1.5 H, Ac); C NMR (150 MHz,
CDCl
3
(
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28.3 (5C), 128.2 (2C), 128.1, 128.0 (2C), 127.9 (2C), 127.8 (2C), 127.7 (6C), 127.6 (4C), 127.5
(2C), 127.4 (2C), 127.3 (2C), 127.1, 106.6, 106.3, 100.5, 100.4, 99.5, 98.5, 91.4, 89.1, 86.0, 85.7,
84.1, 84.0, 83.99, 83.9, 83.8, 83.4, 83.0, 82.9, 81.9, 81.5, 81.34, 81.31, 79.8, 79.3, 78.7, 78.1, 75.12,
75.11, 75.08, 74.5, 74.3, 74.1, 73.29, 73.28, 73.26, 73.23, 72.5, 72.4, 72.3, 72.28, 72.27, 72.25,
7
2.2, 71.94, 71.9, 71.8, 70.0, 69.9, 69.50, 69.4, 69.0, 68.7, 68.6, 66.3, 65.4, 21.1, 21.06, 21.02, 20.8,
+
2
0.7; MALDI-TOF MS m/z: calcd for C115
-Azidopropyl
(29). To a mixture of 28 (500 mg, 0.996 mmol), 3-azido-1-propanol (121 mg, 1.20 mmol), and
H
122
O
24SNa [M + Na] 1941.79, found 1941.47.
3
2-O-Acetyl-3-O-benzyl-5-O-tert-butydimethylsilyl-α-D-arabinofuranoside
MS AW-300 (200 mg) in dry CH
2
Cl
2
(6 mL) were added NIS (247 mg, 1.10 mmol) and AgOTf
o
o
(
26 mg, 0.10 mmol) at -20 C under a N
2
atmosphere. The reaction mixture was stirred at -20 C
for 40 min, and then slowly warmed up to rt and neutralized with triethylamine. The mixture was
diluted with CH Cl (30 mL), filtered through a pad of Celite, and concentrated. Purification of
the residue by silica gel column chromatography with petroleum ether and ethyl acetate (10:1) as
2
2
26
D
1
the eluents gave 29 (403 mg, 84%) as colorless syrup. [α]
MHz, CDCl ): δ 7.35-7.26 (m, 5 H, Ph), 5.10 (s, 1 H, H-2), 4.97 (s, 1 H, H-1), 4.69 (d, J = 12.0 Hz,
H, Bn), 4.55 (d, J = 12.0 Hz, 1 H, Bn), 4.11-4.09 (m, 1 H, H-4), 3.90 (d, J = 4.8 Hz, 1 H, H-3),
3.81-3.77 (m, 1 H, -OCH CH -), 3.75-3.70 (m, 2 H, H-5a,b), 3.52-3.49 (m, 1 H, -OCH CH -),
-), 0.87 (s, 9 H, tBu),
): δ 170.0, 137.8, 128.3,
3
+66.4 (c 1.3, CHCl ); H NMR (600
3
1
2
2
2
2
3
0
1
2 3 2 2
.42-3.38 (m, 2 H, -CH N ), 2.06 (s, 3 H, Ac), 1.88-1.83 (m, 2 H, -OCH CH
13
.04 (s, 3 H, SiMe), 0.03 (s, 3 H, SiMe); C NMR (150 MHz, CDCl
3
27.8, 127.7, 106.0 (C-1), 83.6, 82.9, 81.8, 72.1, 63.7, 62.4, 48.3, 28.9, 25.8, 20.9, 18.3, -5.3, -5.4;
+
ESI-TOF HRMS m/z: calcd for C23
H
41
N
4
O
6
Si [M + NH
4
] 497.2790, found 497.2794.
3
-Azidopropyl 2-O-Acetyl-3-O-benzyl-α-D-arabinofuranoside (30). To a solution of 29 (330
mg, 0.69 mmol) and TBAF (0.83 mmol) in THF (5.8 mL) was added AcOH (79 µL, 1.38 mmol).
The solution was stirred at rt for 6 h and then concentrated. The residue was purified by column
chromatography (petroleum ether-ethyl acetate 2:1) to give 30 (230 mg, 92%) as colorless syrup.
2
6
1
[α]
D
3 3
+116.8 (c 1.0, CHCl ); H NMR (600 MHz, CDCl ): δ 7.35-7.27 (m, 5 H, Ph), 5.10 (d, J =
1
.2 Hz, 1 H, H-2), 4.98 (s, 1 H, H-1), 4.73 (d, J = 12.0 Hz, 1 H, Bn), 4.54 (d, J = 11.4 Hz, 1 H,
2
4
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