Molecules 2019, 24, 583
11 of 17
25
9b (180 mg, 60%) as colorless oils. 9a: [α]
D
= +90.43 (c = 0.16 in CHCl3); IR (neat, cm−1): 3133,
2959, 2873, 2360, 2342, 1647, 1458, 1401, 1269, 1142, 1064, 1020, 953, 860, 669, 549; 1H-NMR (CDCl3)
δ
6.03–5.85 (m, 1H), 5.31 (dd, J = 17.0, 1.9 Hz, 1H), 5.26–5.13(m, 2H), 4.63 (t, J = 4.7 Hz, 1H), 4.50–4.41
(m, 1H), 4.22–4.02 (m, 3H), 4.01–3.90 (m, 2H), 3.89–3.78 (m, 1H), 3.63–3.49 (m, 2H), 3.04 (d, J = 7.4 Hz
,
1H), 1.74–1.53 (m, 2H), 1.38 (q, J = 7.5 Hz, 2H), 0.93 (t, J = 7.3 Hz, 3H). 13C-NMR (CDCl3)
δ 134.1,
117.6, 103.1, 88.0, 77.9, 77.7, 77.2, 71.4, 68.1, 67.9, 31.2, 18.9, 13.5. HR-ESIMS m/z [M + H]+: calcd for
25
C13H23O5: 259.1467; found: 259.1465. 9b: [
α
]
= +8.19 (c = 0.12 in CHCl3); IR (neat, cm−1): 3449,
D
3130, 2960, 2936, 2872, 2382, 1648, 1459, 1400, 1315, 1268, 1116, 1085, 1018, 942, 888, 843, 787, 651, 595,
553, 450; 1H-NMR (CDCl3)
6.03–5.85 (m, 1H), 5.44–5.26 (m, 1H), 5.25–5.16 (m, 1H), 5.02 (s, 1H), 4.83
δ
(t, J = 4.7 Hz, 1H), 4.43 (d, J = 4.7 Hz, 1H), 4.30–4.11 (m, 2H), 4.08–3.90 (m, 3H), 3.90–3.76 (m, 2H),
3.67 (d, J = 3.7 Hz, 1H), 3.44–3.31 (m, 1H), 1.64–1.51 (m, 2H), 1.41–1.30 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H).
13C-NMR (CDCl3)
δ 134.4, 117.4, 109.8, 87.6, 81.3, 80.4, 78.5, 71.1, 69.1, 67.8, 31.3, 19.3, 13.8. HR-ESIMS
m/z [M + H]+: calcd for C13H23O5: 259.1467; found: 259.1469.
4.2.9. Synthesis of Butyl 3,6-anhydro-2-O-nitro-5-O-allyl-α-D-glucofuranoside (2MNS-3) and Butyl
3,6-anhydro-2-O-nitro-5-O-allyl-β-D-glucofuranoside (2MNS-4)
◦
Fuming nitric acid (0.25 mL) was added to acetic anhydride (1 mL) at 0 C. After stirring for
10 min, the solution of 9a (60 mg, 0.23 mmol) in Ac2O (1 mL) ◦was added into the acetic anhydride
solution of fuming nitric acid. The mixture was stirred at 0 C for 15 min and then poured into
ice-water and extracted with EtOAc. The organic layer was washed with brine, dried with Na2SO4 and
then concentrated under reduced pressure to give a crude product, which on column chromatography
(hexane/EtOAc:20:1) gave 2MNS
IR (neat, cm−1): 3441, 3335, 3131, 1660, 1640, 1612, 1454, 1400, 1282, 1138, 1121, 1070, 997, 955, 863, 619,
563, 538, 517; 1H-NMR (CDCl3)
6.04–5.87 (m, 1H), 5.46 (d, J = 4.2 Hz, 1H), 5.40–5.18 (m, 2H), 5.07–4.99
-3 (56 mg, 80%) as a colorless oil. [α]
25 = +129.68 (c = 0.11 in CHCl3);
D
δ
(m, 1H), 4.77–4.70 (m, 1H), 4.68–4.55 (m, 1H), 4.23–4.07 (m, 2H), 4.07–3.95 (m, 2H), 3.83–3.73 (m, 1H),
3.72–3.59 (m, 1H), 3.49–3.38 (m, 1H), 1.68–1.47 (m, 2H), 1.46–1.16 (m, 2H), 0.90 (t, J = 7.3 Hz, 3H).
13C-NMR (CDCl3)
δ
134.1, 118.2, 102.0, 86.3, 82.9, 77.6, 76.7, 71.9, 68.4, 68.3, 31.2, 19.0, 13.6. HR-ESIMS
m/z [M + H]+: calcd for C13H22NO7: 304.1318; found: 304.1321.
In a similar manner, 2MNS
-
4
(188 mg, 80% yield) was obtained as a colorless oil from 9b (200 mg,
25
0.77 mmol). [
α
]
= +24.87 (c = 0.13 in CHCl3); IR (neat, cm−1): 3441, 3132, 1654, 1613, 1454, 1400,
D
1302, 1270, 1138, 1119, 1071, 994, 953, 845, 618, 564, 537, 517; 1H-NMR (CDCl3)
δ 6.02–5.85 (m, 1H),
5.34 (q, J = 1.6 Hz, 1H), 5.26–5.18 (m, 2H), 5.15 (s, 1H), 4.81 (t, J = 4.8 Hz, 1H), 4.62 (d, J = 5.1 Hz, 1H),
4.25–4.13 (m, 1H), 4.08–3.96 (m, 3H), 3.95–3.84 (m, 2H), 3.47–3.37 (m, 1H), 1.65–1.53 (m, 2H), 1.43–1.33
(m, 2H), 0.92 (t, J = 7.3 Hz, 3H). 13C-NMR (CDCl3)
δ 134.4, 117.6, 105.7, 90.0, 83.7, 81.7, 78.2, 71.3, 69.5,
68.2, 31.2, 19.3, 13.9. HR-ESIMS m/z [M + H]+: calcd for C13H22NO7: 304.1318; found: 304.1320.
4.2.10. Synthesis of Butyl 3,6-anhydro-2-O-nitro-α-D-glucofuranoside (2MNS-5) and Butyl
3,6-anhydro-2-O-nitro-β-D-glucofuranoside (2MNS-6)
To a solution of 2MNS-3 (56 mg, 0.19 mmol) in methanol (5 mL) was added 10% Pd-C (18 mg) at
room temperature. After being stirred for 5 h, The catalyst was filtered off and washed with methanol.
The combined filtrate and the washings were condensed under reduced pressure to give a pale yellow
oil, which was then subjected to column chromatography (hexane/EtOAc:20/1
→
hexane/EtOAc:5/1),
to provide 2MNS (29 mg, 60%) as a colorless oil. [
-
5
α]
D
25 = +120.83 (c = 0.11 in CHCl3); IR (neat, cm−1):
3440, 3132, 2454, 1660, 1638, 1616, 1454, 1400, 1283, 1259, 1138, 1120, 1069, 999, 954, 864, 817, 716, 619,
1
564, 537, 517; H-NMR (CDCl3)
δ 5.46 (d, J = 4.1 Hz, 1H), 5.04 (t, J = 3.9 Hz, 1H), 4.74 (dd, J = 5.8,
3.6 Hz, 1H), 4.63 (t, J = 5.6 Hz, 1H), 4.30–4.19 (m, 1H), 3.99 (dd, J = 9.4, 5.8 Hz, 1H), 3.81–3.71 (m, 1H),
3.63 (dd, J = 9.4, 7.0 Hz, 1H), 3.49–3.38 (m, 1H), 2.41 (d, J = 8.0 Hz, 1H), 1.61–1.47 (m, 2H), 1.41–1.28
(m, 2H), 0.90 (t, J = 7.3 Hz, 3H). 13C-NMR (CDCl3)
δ
102.6, 85.9, 82.6, 78.2, 72.0, 70.9, 68.7, 31.3, 19.1,
13.7. HR-ESIMS m/z [M + H]+: calcd for C10H18NO7: 264.1005; found: 264.1010.