PAPER
Lipase-Catalysed Selective Synthesis of Sucrose Mixed Diesters
461
Hz, 1 H, H-3’), 4.10 4.15 (m, 1 H, H-5), 4.18 (d, J = 12.0 Hz, 1 H,
H-1’b), 4.31 (dd, J = 12.0, 5.1 Hz, 1 H, H-6b), 4.36 (dd, J = 11.9,
13C NMR (75 MHz): = 13.5 (CH ), 25.1 (CH ), 22.8, 29.2 29.8,
3
2
32.1 (CH ), 34.0 (CH ), 61.5 (C-6), 62.5 (C-1’), 65.7 (C-6’), 70.5
2
2
7
.3 Hz, 1 H, H-6’b), 4.37 (d, J = 12.1 Hz, 1 H, H-1’a), 4.42 (dd,
J = 11.9, 3.4 Hz, 1 H, H-6’a), 4.46 (dd, J = 12.0, 2.1, 1 H, H-6a),
.39 (d, J = 3.8 Hz, 1 H, H-1), 5.64, 6.14 (2s, 4 H, C=CH2).
(C-4), 72.1 (C-2), 73.3 (C-5), 73.7 (C-3), 75.1 (C-4’), 77.4 (C-3’),
79.8 (C-5’), 93.0 (C-1), 103.2 (C-2’), 173.6, 174.4 (C=O).
5
HRMS: m/z calcd for (M + Na): 813.5328. Found: 813.5340.
13C NMR (125 MHz):
= 13.4 (CH ), 17.5 (CH ), 25.1 (CH ), 22.7,
2
6
3
3
2
Anal. calcd for C H O : C, 63.8; H, 9.9; O, 26.3. Found: C, 63.8;
4
2
78 13
9.2 29.7, 32.1 (CH ), 34.0 (CH ), 62.8 (C-1’), 64.2 (C-6), 65.9 (C-
2 2
H, 9.6; O, 26.4.
’), 70.8 (C-5), 71.0 (C-4), 72.0 (C-2), 73.6 (C-3), 75.3 (C-4’), 77.7
1
[
2
(
1
C-3’), 79.8 (C-5’), 93.0 (C-1), 103.5 (C-2’), 125.5, 125.6 (C=CH2),
36.5, 136.7 (C=CH ), 167.5, 167.8, 173.7 (C=O).
]D20 +37.0 (c = 1, THF).
2
1H NMR (300 MHz): = 0.86 0.96 (m, 6 H, CH ), 1.20 1.42 (m,
HRMS: m/z calcd for (M + Li): 667.3517. Found 667.3526.
3
3
2
2 H, CH ), 1.57 1.72 (m, 4 H, CH ), 1.99 2.12 (m, 4 H, CH ),
2
2
2
Anal. calcd for C H O 0.5 H O: C, 57.4; H, 7.9; O, 34.6. Found:
C, 57.4; H, 8.1; O, 34.2.
32
52 14
2
.31 2.40 (m, 4 H, CH ), 3.36 (t, J = 9.2 Hz, 1 H, H-4), 3.42 (dd,
2
J = 9.8, 3.8 Hz, 1 H, H-2), 3.69 (t, J = 9.3 Hz, 1 H, H-3), 3.73 (dd,
J = 12.3, 3.7 Hz, 1 H, H-6b), 3.80 3.89 (m, 2 H, H-5, H-6a), 3.90
(dt, J = 7.9, 3.0 Hz, 1 H, H-5’), 4.03 (t, J = 8.3 Hz, 1 H, H-4’), 4.08
(d, J = 8.5 Hz, 1 H, H-3’), 4.12 (d, J = 12.0 Hz, 1 H, H-1’b), 4.33
8
[
]D20 +46.0 (c = 1, MeOH).
1
H NMR (500 MHz): 0.91 (t, J = 9.0 Hz, 3 H, CH ), 1.26 1.40 (m,
3
(
4
dd, J = 11.8, 3.5 Hz, 1 H, H-6’b), 4.39 (d, J = 12.0 Hz, 1 H, H-1’a),
.41 (dd, J = 11.8, 7.9 Hz, 1 H, H-6’a), 5.36 (3, 3 H, H-1, HC=CH).
1
6 H, CH ), 1.58 1.68 (m, 2 H, CH ), 1.98 (s, 3 H, CH ), 2.37 (t,
2
2
3
J = 7.3 Hz, 2 H, CH ), 3.36 (t, J = 9.0 Hz, 1 H, H-4), 3.43 (dd,
J = 9.8, 3.8 Hz, 1 H, H-2), 3.70 (t, J = 8.9 Hz, 1 H, H-3), 3.73 (dd,
J = 12.1, 5.3 Hz, 1 H, H-6b), 3.82 3.93 (m, 3 H, H-5, H-5’, H-6a),
2
13C NMR (75 MHz): = 13.5 (CH ), 25.0 (CH ), 27.2 (CH ), 22.7,
3 2 2
29.2 29.9, 32.1, (CH ), 34.0 (CH ), 61.5 (C-6), 62.4 (C-1’), 65.7
2
2
4
(
6
.05 (t, J = 8.3 Hz, 1 H, H-4’), 4.11 (d, J = 8.5 Hz, 1 H, H-3’), 4.25
d, J = 12.0 Hz, 1 H, H-1’b), 4.34 (dd, J = 11.8, 3.2 Hz, 1 H, H-
’b), 4.40 (d, J = 12.2 Hz, 1 H, H-1’a), 4.42 (dd, J = 11.8, 7.6 Hz, 1
(C-6’), 70.5 (C-4), 72.0 (C-2), 73.3 (C-5), 73.7 (C-3), 75.1 (C-4’),
77.4 (C-3’), 79.8 (C-5’), 93.0 (C-1), 103.2 (C-2’), 129.8, 129.9
(HC=CH), 173.6, 174.4 (C=O).
H, H-6’a), 5.39 (d, J = 3.8 Hz, 1 H, H-1), 5.68, 6.17 (2 s, 2 H,
C=CH2).
HRMS: m/z calcd for (M + Na): 783.4888. Found: 783.4870.
Anal. calcd for C H O 0.6 H O: C, 62.2; H, 9.6. Found: C, 62.2;
13C NMR (125 MHz):
40
72 13
2
= 13.4 (CH ), 17.5 (CH ), 25.0 (CH ), 22.7,
3
3
2
H, 9.9.
2
6
9.2 29.7, 32.1 (CH ), 33.9 (CH ), 61.5 (C-6), 63.1 (C-1’), 65.5 (C-
’), 70.6 (C-4), 72.1 (C-2), 73.3, 73.7 (C-5, C-3), 75.1 (C-4’), 77.6
2 2
1
[
4
]D20 +70.0 (c = 1, THF).
(
(
C-3’), 79.8 (C-5’), 93.0 (C-1), 103.3 (C-2’), 125.7 (C=CH), 136.5
C=CH), 167.0, 174.5 (C=O).
1H NMR (500 MHz): = 0.92 (t, J = 7.1 Hz, 3 H, CH ), 1.26 1.41
3
(
m, 24 H, CH ), 1.60 1.68 (m, 2 H, CH ), 2.39 (t, J = 7.5 Hz, 2 H,
2 2
HRMS: m/z calcd for (M + Li): 559.3255. Found: 559.3269.
CH ), 3.29 (t, J = 9.4 Hz, 1 H, H-4), 3.41 (s, 3 H, OCH ), 3.39 (dd,
2
3
Anal. calcd for C H O 1 H O: C, 55.1; H, 8.2. Found: C, 55.0;
28
48 13
2
J = 9.6, 3.8 Hz, 1 H, H-2), 3.63 (t, J = 9.2 Hz, 1 H, H-3), 3.70 3.75
m, 1 H, H-5), 4.21 (dd, J = 11.8, 6.1 Hz, 1 H, H-6b), 4.41 (dd,
J = 11.8, 2.2 Hz, 1 H, H-6a), 4.67 (d, J = 3.8 Hz, 1 H, H-1).
H, 7.9.
(
1
[
0
]D20 +35.0 (c = 1, THF).
13C NMR (125 MHz):
32.0 (CH ), 34.1 (CH ), 64.6 (OCH ), 63.8 (C-6), 70.2 (C-5), 71.0
= 13.3 (CH ), 25.0 (CH ), 22.6, 29.1 29.7,
3
2
1H NMR (500 MHz): = 0.82 0.97 (m, 6 H, CH ), 1.20 1.43 (m,
3
2 2 3
2
2
8 H, CH ), 1.50 1.70 (m, 4 H, CH ), 1.97 2.11 (m, 4 H, CH ),
(C-4), 72.6 (C-2), 74.1 (C-3), 100.3 (C-1), 174.4 (C=O).
2
2
2
.25 2.42 (m, 4 H, CH ), 3.36 (t, J = 9.2 Hz, 1 H, H-4), 3.42 (dd,
2
HRMS: m/z calcd for (M + Na): 455.2986. Found: 455.2984.
J = 9.8, 3.8 Hz, 1 H, H-2), 3.69 (t, J = 9.3 Hz, 1 H, H-3), 3.73 (dd,
J = 12.3, 3.7 Hz, 1 H, H-6b), 3.80 3.85 (m, 2 H, H-5, H-6a), 3.90
Anal. calcd. for C H O : C, 63.9; H, 10.3. Found: C, 63.8; H, 10.5.
23 44
7
(
(
(
dt, J = 7.9, 3.0 Hz, 1 H, H-5’), 4.03 (t, J = 8.3 Hz, 1 H, H-4’), 4.08
d, J = 8.5 Hz, 1 H, H-3’), 4.12 (d, J = 12.0 Hz, 1 H, H-1’b), 4.33
dd, J = 11.8, 3.5 Hz, 1 H, H-6’b), 4.39 (d, J = 12.0 Hz, 1 H, H-1’a),
1
[
6
]D20 +21.0 (c = 1, THF).
1H NMR (500 MHz): = 0.92 (t, J = 7.0 Hz, 6 H, CH ), 1.26 1.46
3
4
.41 (dd, J = 11.8, 7.9 Hz, 1 H, H-6’a), 5.32 5.43 (m, 3 H, H-1,
(
m, 44 H, CH ), 1.60 1.68 (m, 4 H, CH ), 2.39 (t, J = 7.5 Hz, 2 H,
2
2
HC=CH).
13C NMR (125 MHz):
2
6
CH ), 3.24 (t, J = 9.4 Hz, 1 H, H-2’), 3.28 (t, J = 9.4 Hz, 1 H, H-4),
3.37 3.41 (m, 1 H, H-5’), 3.47 (dd, J = 9.7, 3.8 Hz, 1 H, H-2), 3.51
(t, J = 9.1 Hz, 1 H, H-4’), 3.53 3.58 (m, 1 H, OCH ), 3.62 (t,
J = 9.1 Hz, 1 H, H-3’), 3.62 (t, J = 9.3 Hz, 1 H, H-3), 3.82 (dd,
J = 12.5, 5.1 Hz, 1 H, H-6’b), 3.88 3.94 (m, 3 H, H-6’a, OCH , H-
5
2
= 13.6 (CH ), 25.1 (CH ), 27.1 (CH ), 22.8,
3 2 2
9.2 29.8, 32.1 (CH ), 34.0 (CH ), 61.5 (C-6), 62.5 (C-1’), 65.7 (C-
2 2
2
a
’), 70.5 (C-4), 72.1 (C-2), 73.3 (C-5), 73.7 (C-3), 75.1 (C-4’), 77.4
C-3’), 79.8 (C-5’), 93.0 (C-1), 103.3 (C-2’), 129.8, 129.9
(
(
2
a
HC=CH), 173.6, 174.4 (C=O).
), 4.17 (dd, J = 11.8, 6.8 Hz, 1 H, H-6b), 4.29 (d, J = 7.8 Hz, 1 H,
H-1’), 4.42 (dd, J = 11.8, 2.0 Hz, 1 H, H-6a), 5.13 (d, J = 3.8 Hz, 1
H, H-1).
Anal. calcd for C H O : C, 62.3; H, 9.4. Found: C, 62.5; H, 9.5.
38
68 13
1
[
1
13C NMR (125 MHz):
2.1 (CH ), 34.0 (CH ), 61.4 (C-6’), 64.0 (C-6), 70.0 (OCH ), 70.6
= 13.5 (CH ), 25.0 (CH ), 22.8, 29.3 29.9,
3 2
]D20 +36.0 (c = 1, THF).
3
1H NMR (300 MHz): = 0.82 0.97 (m, 6 H, CH ), 1.18 1.44 (m,
2
2
2
3
(
7
C-4), 71.3 (C-5), 73.1 (C-2), 73.6 (C-2’), 74.0 (C-3), 75.6 (C-5’),
6.8 (C-3’), 81.1 (C-4’), 102.1 (C-1), 103.3 (C-1’), 174.5 (C=O).
4
3
3
6
4 H, CH ), 1.53 1.72 (m, 4 H, CH ), 2.28 2.46 (m, 4 H, CH ),
2
2
2
.32 (t, J = 9.2 Hz, 1 H, H4), 3.35 (dd, J = 9.8, 3.8 Hz, 1 H, H-2),
.65 (t, J = 9.3 Hz, 1 H, H-3), 3.69 (dd, J = 12.3, 3.7 Hz, 1 H, H-
b), 3.78 3.87 (m, 2 H, H-5, H-6a), 3.89 (dt, J = 7.9, 3.0 Hz, 1 H,
HRMS: m/z calcd for (M + Na): 771.5297. Found: 771.5234.
Anal. calcd for C H O 0.6 H O: C, 63.2; H, 10.3; O, 26.5.
4
0
76 12
2
H-5’), 4.02 (t, J = 8.3 Hz, 1 H, H-4’), 4.06 (d, J = 8.5 Hz, 1 H, H-
’), 4.11 (d, J = 12.0 Hz, 1 H, H-1’b), 4.34 (dd, J = 11.8, 3.5 Hz, 1
Found: C, 63.1; H, 10.4; O, 26.2.
3
1
[
8
H, H-6’b), 4.39 (d, J = 12.0 Hz, 1 H, H-1’a), 4.40 (dd, J = 11.8, 7.9
Hz, 1 H, H-6’a), 5.36 (d, J = 3.7 Hz, 1 H, H-1).
]D20 +31.0 (c = 1, THF).
Synthesis 2001, No. 3, 458–462 ISSN 0039-7881 © Thieme Stuttgart · New York