470
F. Nisic, A. Bernardi / Carbohydrate Research 346 (2011) 465–471
3.8.2. N-(3-Methylbutanoyl)-b-
D
-galactofuranosylamide (6b)
3.8.7. N-Pentanoyl-a-D-galactofuranosylamide (7a)
The compound was purified by flash chromatography (CHCl3–
The compound was purified by flash chromatography (CHCl3–
MeOH 85:15) yield = 53%. ½a D25
ꢂ
ꢁ24.5 (c 1, MeOH). 1H NMR
MeOH 80:20) yield = 60%. ½a D25
ꢂ
+18.1 (c 1, MeOH). 1H NMR
(400 MHz, CD3OD, 25 °C): d = 5.40 (d, J1,2 = 5.2 Hz, 1H, H-1), 4.15
(t, J2,3 = 5.8, J3,4 = 6.4 Hz, 1H, H-3), 3.97 (t, J1,2 = 5.2, J2,3 = 5.8 Hz,
1H, H-2), 3.92 (dd, J3,4 = 6.4, J4,5 = 2.8 Hz, 1H, H-4), 3.71–3.65 (m,
1H, H-5), 3.63–3.58 (m, 2H, H-6, H-60), 2.35 (d, J = 7.2 Hz, 2H,
CH2), 1.01 (d, J = 6.4 Hz, 3H, CH3), 0.97 (d, J = 6 Hz, 3H, CH3); 13C
NMR (100 MHz, CD3OD, 25 °C): d = 176.6, 85.6 (C-1), 83.7 (C-4),
81.2 (C-2), 77.5 (C-3), 72.7 (C-5), 64.4 (C-6), 46.5 (CH2), 22.9
(CH3), 22.7 (CH3). FT-ICR (ESI) calcd for C11H21N1O6 [M+Na]+
286.12611, found 286.12584.
(400 MHz, CD3OD, 25 °C): d = 5.69 (d, J1,2 = 4.4 Hz, 1H, H-1), 4.13
(t, J2,3 = 3.4, J3,4 = 3.6 Hz, 1H, H-3), 3.88 (dd, J1,2 = 4.4, J2,3 = 3.4 Hz,
1H, H-2), 3.80 (dd, J3,4 = 3.6, J4,5 = 3 Hz, 1H, H-4), 3.74 (ddd,
0
J4,5 = 3, J5,6 = 6, J5,6 = 6.8 Hz, 1H, H-5), 3.62 (dd, J5,6 = 6,
0
0
0
J6,6 = 11.6 Hz, 1H, H-6), 3.57 (dd, J5,6 = 6.8, J6,6 = 11.6 Hz, 1H, H-
60), 2.29 (t, J = 7.6 Hz, 2H, CH2), 1.64–1.56 (m, 2H, CH2), 1.43–1.32
(m, 2H, CH2), 0.95 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (100 MHz,
CD3OD, 25 °C): d = 176.7, 84.4 (C-4), 82.2 (C-1), 78.5 (C-3), 77.4
(C-2), 73 (C-5), 64.3 (C-6), 37 (CH2), 28.9 (CH2), 23.5 (CH2), 14.3
(CH3). FT-ICR (ESI) calcd for C11H21N1O6 [M+Na]+ 286.12611, found
286.12597.
3.8.3. N-3-Methyl-2-butenoyl-b-D-galactofuranosylamide (6c)
The compound was purified by flash chromatography (CHCl3–
MeOH 85:15) yield = 48%. ½a D25
ꢂ
ꢁ27.8 (c 0.2, MeOH). 1H NMR
3.8.8. N-(3-Methylbutanoyl)-a-D-galactofuranosylamide (7b)
The compound was purified by flash chromatography (CHCl3/
(400 MHz, CD3OD, 25 °C): d = 5.74 (s, 1H, CH), 5.41 (d, J1,2 = 5.6 Hz,
1H, H-1), 4.15 (t, J2,3 = 5.8, J3,4 = 6.4 Hz, 1H, H-3), 3.96 (t, J1,2 = 5.6,
J2,3 = 5.8 Hz, 1H, H-2), 3.90 (dd, J3,4 = 6.4, J4,5 = 2.8 Hz, 1H, H-4),
3.68–3.63 (m, 1H, H-5), 3.61–3.57 (m, 2H, H-6, H-60), 2.15 (s, 3H,
CH3), 1.89 (s, 3H, CH3); 13C NMR (100 MHz, CD3OD, 25 °C):
d = 170.2, 154.3, 119.3 (CH), 85.4 (C-1), 83.4 (C-4), 81.1 (C-2), 77.5
(C-3), 72.8 (C-5), 64.4 (C-6), 27.5 (CH3), 20.3 (CH3). FT-ICR (ESI) calcd
for C11H21N1O6 [M+Na]+ 284.11046, found 284.11027.
MeOH 80:20) yield = 57%. ½a D25
ꢂ
+33.4 (c 1, MeOH). 1H NMR
(400 MHz, CD3OD, 25 °C): d = 5.72 (d, J1,2 = 4.4 Hz, 1H, H-1), 4.16
(t, J2,3 = 3.2, J3,4 = 3.6 Hz, 1H, H-3), 3.92 (dd, J1,2 = 4.4, J2,3 = 3.2 Hz,
1H, H-2), 3.84 (dd, J3,4 = 3.6, J4,5 = 3.2 Hz, 1H, H-4), 3.78 (ddd,
0
0
J4,5 = 3.2, J5,6 = 5.6, J5,6 = 6.8 Hz, 1H, H-5), 3.65 (dd, J5,6 = 5.6, J6,6
=
11.2 Hz, 1H, H-6), 3.61 (dd, J5,6 = 6.8, J6,6 = 11.2 Hz, 1H, H-60),
2.18 (d, J = 6.4 Hz, 2H, CH2), 2.16–2.08 (m, 1H, CH), 1.01 (d,
J = 2.4 Hz, 3H, CH3), 0.99 (d, J = 2.4 Hz, 3H, CH3); 13C NMR
(100 MHz, CD3OD, 25 °C): d = 176, 85.6 (C-4), 84.5 (C-1), 82.2 (C-
3), 77.4 (C-2), 73 (C-5), 64.3 (C-6), 46.5 (CH2), 27.3 (CH), 22.9
(CH3). FT-ICR (ESI) calcd for C11H21N1O6 [M+Na]+ 286.12611, found
286.12591.
0
0
3.8.4. N-Palmitoyl-b-D-galactofuranosylamide (6d)
The compound was purified by flash chromatography (CHCl3–
MeOH 90:10) yield = 60%. ½a D25
ꢂ
ꢁ37.3 (c 1, MeOH). 1H NMR
(400 MHz, CD3OD, 25 °C): d = 5.40 (d, J1,2 = 5.2 Hz, 1H, H-1), 4.15
(t, J2,3 = 6, J3,4 = 6 Hz, 1H, H-3), 3.96 (t, J1,2 = 5.2, J2,3 = 5.6 Hz, 1H,
H-2), 3.93 (dd, J3,4 = 6.4, J4,5 = 2.8 Hz, 1H, H-4), 3.70–3.65 (m, 1H,
H-5), 3.63–3.58 (m, 2H, H-6, H-60), 2.24 (t, J = 8 Hz, 2H, CH2), 1.63
(m, 2H, CH2), 1.41–1.25 (m, 24H, 12 ꢀ CH2), 0.92 (t, J = 6.8 Hz,
3H, CH3); 13C NMR (100 MHz, CD3OD, 25 °C): d = 177.1, 85.7 (C-
1), 83.8 (C-4), 81.2 (C-2), 77.6 (C-3), 72.8 (C-5), 64.4 (C-6), 37.4,
33.2, 30.9, 30.7, 30.6, 30.4, 26.8, 23.8, 14.6 (CH3). FT-ICR (ESI) calcd
for C22H43N1O6 [M+Na]+ 440.29826; found 440.29844.
3.8.9. N-(3-Methyl-2-butenoyl)-a-D-galactofuranosylamide (7c)
The compound was purified by flash chromatography (CHCl3–
MeOH 85:15) yield = 51%. ½a D25
ꢂ
+30.2 (c 0.8, MeOH). 1H NMR
(400 MHz, CD3OD, 25 °C): d = 5.86 (s, 1H, CH), 5.77 (d, J1,2 = 4 Hz,
1H, H-1), 4.17 (t, J2,3 = 3.2, J3,4 = 3.6 Hz, 1H, H-3), 3.94 (dd, J1,2 = 4,
J2,3 = 3.2 Hz, 1H, H-2), 3.85 (br t, J3,4 = 3.6, J4,5 = 3.2 Hz, 1H, H-4),
0
3.79 (ddd, J4,5 = 3.2, J5,6 = 6, J5,6 = 6.8 Hz, 1H, H-5), 3.68 (dd,
0
0
0
J5,6 = 6, J6,6 = 11.2 Hz, 1H, H-6), 3.62 (dd, J5,6 = 6.8, J6,6 = 11.2 Hz,
1H, H-60), 2.20 (s, 3H, CH3), 1.94 (s, 3H, CH3); 13C NMR (100 MHz,
CD3OD, 25 °C): d = 169.5, 154.2, 119.4 (CH), 84.4 (C-4), 82.1 (C-1),
78.7 (C-3), 77.5 (C-2), 73.1 (C-5), 64.4 (C-6), 27.4 (CH3), 20.3
(CH3). FT-ICR (ESI) calcd for C11H21N1O6 [M+Na]+ 284.11046; found
284.11044.
3.8.5. N-Capryloyl-b-D-galactofuranosylamide (6e)
The compound was purified by flash chromatography (CHCl3–
MeOH 85:15) yield = 56%. ½a D25
ꢂ
ꢁ50.4 (c 0.9, MeOH). 1H NMR
(400 MHz, CD3OD, 25 °C): d = 5.42 (d, J1,2 = 5.2 Hz, 1H, H-1), 4.17
(t, J2,3 = 5.8, J3,4 = 6.4 Hz, 1H, H-3), 3.98 (t, J1,2 = 5.2, J2,3 = 5.8 Hz,
1H, H-2), 3.95 (dd, J3,4 = 6.4, J4,5 = 2.8 Hz, 1H, H-4), 3.73–3.68 (m,
1H, H-5), 3.65–3.59 (m, 2H, H-6, H-60), 2.28 (t, J = 7.2, J = 8 Hz,
2H, CH2), 1.65 (m, 2H, CH2), 1.47–1.27 (m, 8H, 4 ꢀ CH2), 0.94 (t,
J = 6.8 Hz, 3H, CH3); 13C NMR (100 MHz, CD3OD, 25 °C): d = 177.1,
85.4 (C-1), 83.6 (C-4), 81 (C-2), 77.3 (C-3), 72.6 (C-5), 64.2 (C-6),
37.2, 32.8, 30.2, 30.1, 26.7, 23.6, 14.4 (CH3). FT-ICR (ESI) calcd for
3.8.10. N-Palmitoyl-
The compound was purified by flash chromatography (CHCl3/
MeOH 90:10) yield = 55%.
+9 (c 1, MeOH). 1H NMR
a-D-galactofuranosylamide (7d)
½ ꢂ
a 2D5
(400 MHz, CD3OD, 25 °C): d = 5.74 (d, J1,2 = 4 Hz, 1H, H-1), 4.18 (t,
J2,3 = 3.2, J3,4 = 3.6 Hz, 1H, H-3), 3.94 (dd, J1,2 = 4, J2,3 = 3.2 Hz, 1H,
H-2), 3.85 (br t, J3,4 = 3.6, J4,5 = 2.8 Hz, 1H, H-4), 3.79 (ddd,
C
14H27N1O6 [M+Na]+ 328.17306, found 328.17317.
0
J4,5 = 2.8, J5,6 = 6, J5,6 = 6.8 Hz, 1H, H-5), 3.67 (dd, J5,6 = 6,
0
0
0
J6,6 = 11.2 Hz, 1H, H-6), 3.63 (dd, J5,6 = 6.8, J6,6 = 11.2 Hz, 1H, H-
60), 2.33 (t, J = 7.2 Hz, 2H, CH2), 1.68 (br t, J = 7.2 Hz, 2H, CH2),
1.44–1.28 (m, 24H), 0.96 (t, J = 6.8 Hz, 3H, CH3); 13C NMR
(100 MHz, CD3OD, 25 °C): d = 176.7, 84.4 (C-4), 82.2 (C-1), 78.5
(C-3), 77.4 (C-2), 73 (C-5), 64.4 (C-6), 37.3, 33.2, 30.9, 30.8, 30.6,
30.4, 26.8, 23.9, 14.6 (CH3). FT-ICR (ESI) calcd for C22H43N1O6
[M+Na]+ 440.29826, found 440.29797.
3.8.6. N-Citronelloyl-b- -galactofuranosylamide (6f)
D
The compound was purified by flash chromatography (CHCl3–
MeOH 90:10) yield = 51%. ½a D25
ꢂ
ꢁ55.8 (c 0.9, MeOH). 1H NMR
(400 MHz, CD3OD, 25 °C): d = 5.45 (d, J1,2 = 5.2 Hz, 1H, H-1), 5.16
(t, J = 6.8 Hz, 1H, CH) 4.20 (t, J2,3 = 5.6, J3,4 = 6.2 Hz, 1H, H-3), 4.01
(t, J1,2 = 5.2, J2,3 = 5.6 Hz, 1H, H-2), 3.97 (dd, J3,4 = 6.2, J4,5 = 2.8 Hz,
1H, H-4), 3.71 (ddd, J4,5 = 2.8, J = 6, J = 6.8 Hz, 1H, H-5), 3.68–3.63
(m, 2H, H-6, H-60), 2.29 (dd, J = 13.6, J = 6 Hz, 1H, Ha, CH2), 2.18–
1.98 (m, 4H), 1.73 (s, 3H, CH3), 1.67 (s, 3H, CH3), 1.48–1.40 (m,
1H), 1.33–1.22 (m, 1H), 1.01 (d, J = 6.4 Hz, 3H, CH3); 13C NMR
(100 MHz, CD3OD, 25 °C): d = 176.6, 132.4, 125.7, 85.7 (C-1), 83.8
(C-4), 81.2 (C-2), 77.6 (C-3), 72.8 (C-5), 64.4 (C-6), 44.9, 38.1,
30.9, 26.6, 26, 19.9, 17.9. FT-ICR (ESI) calcd for C16H29N1O6
[M+Na]+ 354.18871, found 354.18866.
3.8.11. N-Capryloyl-a-D-galactofuranosylamide (7e)
The compound was purified by flash chromatography (CHCl3–
MeOH 85:15) yield = 63%. ½a D25
ꢂ
+12.2 (c 1, MeOH). 1H NMR
(400 MHz, CD3OD, 25 °C): d = 5.68 (d, J1,2 = 4.4 Hz, 1H, H-1), 4.12
(t, J2,3 = 3.6, J3,4 = 3.2 Hz, 1H, H-3), 3.87 (dd, J1,2 = 4.4, J2,3 = 3.6 Hz,
1H, H-2), 3.79 (t, J3,4 = 3.2, J4,5 = 2.8 Hz, 1H, H-4), 3.73 (ddd,
0
J4,5 = 2.8, J5,6 = 6, J5,6 = 6.8 Hz, 1H, H-5), 3.61 (dd, J5,6 = 6,