Supporting Information

Protection-free Synthesis of Alkyl Glycosides under Hydrogenolytic Conditions

Masaki Ishihara, Yuka Takagi, Gefei Li, Masato Noguchi, and Shin-ichiro Shoda*
Graduate School of Engineering, Tohoku University, 6-6-11-514 Aoba, Aoba-ku, Sendai, Miyagi 980-8579

(Received July 11, 2013; CL-130646; E-mail: [email protected])

Copyright © The Chemical Society of Japan

 Supporting Information

Table of Contents

Preparation of glycosyl donors

Synthesis of DBT--glucoside (2a) 2
Synthesis of DBT--melibioside (2b) 2
Synthesis of DBT--maltopentaoside (2c) 2

Glycosylation by using DBT-glycoside as glycosyl donors

Reaction procedure 3
NMR data of glycoside 3
1H NMR and 13C NMR spectra of DBT-gycosides and glycosylated products 5

1
Synthesis of 4,6-dibenzyloxy-1,3,5-triazin-2-yl -D-glucoside (DBT--glucoside) (2a)
2-Chloro-4,6-dibenzyloxy-1,3,5-triazine (12.3 g, 37.5 mmol) was added to a solution of D-glucose
(4.5 g, 25 mmol), N-methylmorpholine (4.13 ml, 37.5 mmol) and ammonia (3.25 ml, 50 mmol, 29%
aqueous solution) in the mixture of acetonitrile and water (125 ml, CH3CN:H2O=50 vol.:50 vol.) and
the resulting mixture was stirred for 3 h at 0 ºC. After concentration in vacuo, the residue was
washed with water and chloroform. The filtrate was concentrated in vacuo to give
4,6-dibenzyloxy-1,3,5-triazin-2-yl -D-glucoside (9.42 g, 20.0 mmol, 80 %).
1H NMR (500 MHz, CD3OD) : δ 7.45-7.31 (10H, m, CH2-Ph), 5.81 (1H, d, H-1, J=8.0 Hz), 5.48 (2H, d,
CH2-Ph, J=13.8 Hz), 5.45 (2H, d, CH2-Ph, J=13.8 Hz), 3.84-3.82 (1H, m, H-6b), 3.67-3.62 (1H, m,
H-6a), 3.50-3.43 (3H, m, H-2, H-4, H-5), 3.39-3.36 (1H, m, H-3)
13C NMR (126 MHz, CD3OD) : δ 174.5 (triazine), 174.1 (triazine), 137.0 (Ph), 129.6 (Ph), 129.5 (Ph),
129.3 (Ph), 99.0 (C-1), 78.9 (C-5), 77.8 (C-2), 74.1 (C-4), 71.2 (CH2-Ph), 71.1 (C-3), 62.4 (C-6).

Synthesis of 4,6- dibenzyloxy-1,3,5-triazin-2-yl β-D-melibioside (DBT-β-melibioside)(2b)

2-Chloro-4,6-dibenzyloxy-1,3,5-triazine (49.2 mg, 0.15 mmol) was added to a solution of
D-melibiose (34.2 mg, 0.1 mmol), N-methylmorpholine (22 μl, 0.2 mmol) and ammonia (15 μl, 0.2
mmol, 28% aqueous solution) in the mixture of acetonitrile and water (2 ml, CH3CN : H2O = 50 vol. :
50 vol.) and the resulting mixture was stirred for 7 h at 0ºC. After concentration in vacuo, the
residue was purified by silica gel column chromatography (CHCl3: CH3OH = 4 : 1 to 2 : 1) to give
4,6-dibenzyloxy-1,3,5-triazin-2-yl β-D-melibioside (41 mg, 0.065 mmol, 65 %).
1H NMR (500 MHz, CD3OD) : δ 7.49-7.33 (10H, m, CH2-Ph), 5.83 (1H, d, H-1, J=7.6 Hz), 5.51 (2H,
d, CH2-Ph, J=14.1 Hz), 5.50 (2H, d, CH2-Ph, J=14.1 Hz), 4.85 (1H, d, H-1’, J=2.3 Hz), 3.95 (1H, q,
H-6b), 3.88-3.83 (2H, m, H-5’, H-4’), 3.77-3.72 (3H, m, H-2, H-3’, H-6a), 3.70-3.63 (3H, m, H-5, H-6’b,
H-6’a), 3.55-3.47 (3H, m, H-2, H-3, H-4);
13C NMR (126 MHz, CD3OD) : δ 174.2 (triazine), 173.8 (triazine), 136.8 (Ph), 129.6 (Ph), 129.4
(Ph), 129.2 (Ph), 99.9 (C-1’), 98.8 (C-1), 77.7 (C-2), 77.1 (C-5), 73.8 (C-4), 72.0 (C-4’), 71.4 (C-3’), 71.2
(CH2-Ph), 70.9 (C-3), 70.8 (C-5’), 70.3 (C-2’), 66.9 (C-6), 62.5 (C-6’).

Synthesis of 4,6-dibenzyloxy-1,3,5-triazin-2-yl -D-maltopentaoside (DBT--maltopentaoside) (2c)

2-Chloro-4,6-dibenzyloxy-1,3,5-triazine (0.6 g, 1.8 mmol) was added to a solution of
D-maltopentaose (1 g, 1.2 mmol), N-methylmorpholine (0.265 ml, 2.4 mmol) and ammonia (0.159 ml,
2.4 mmol, 29% aqueous solution) in the mixture of acetonitrile and water (8 ml, CH3CN:H2O=50
vol.%:50 vol.%) at 0ºC, then the resulting mixture was stirred for 12.5 h at room temperature. After
concentration in vacuo, the residue was washed with ethyl acetate and water. The filtrate was
concentrated in vacuo to give 4,6-dibenzyloxy-1,3,5-triazin-2-yl -D-maltopentaoside (930 mg, 0.83
mmol, 69 %).
1H NMR (400 MHz, DMSO-d6) : δ 7.45-7.18 (10H, m, CH2-Ph), 5.73 (1H, d, H-1, J=8.1 Hz), 5.63 (1H,
d, sugar-OH, J=4.0 Hz), 5.59-5.23 (12H, m, sugar-OH, CH2-Ph), 5.06-4.90 (4H, m, H-1’, H-1’’, H-1’’’,
H-1’’’’), 4.88-4.79 (2H, m, sugar-OH), 4.61-4.41 (5H, m, sugar-OH), 3.69-3.37 (20H, m, sugar-H),
3.37-3.14 (9H, m, sugar-H), 3.07-2.96 (1H, m, sugar-H);
13C NMR (100 MHz, DMSO-d6) : δ 173.2 (triazine), 172.8 (triazine), 136.1 (Ph), 129.0 (Ph), 128.9
2
(Ph), 128.8 (Ph), 101.3-100.9 (4C, C-1’, C-1’’, C-1’’’, C-1’’’’), 97.8 (C-1), 80.1-72.2 (sugar-C), 69.9
(CH2-Ph), 61.3-60.6 (5C, C-6, C-6’, C-6’’, C-6’’’, C-6’’’’).

Reaction procedure using palladium catalyzed hydrogenation

Under hydrogen atmosphere, nucleophile was added to the mixture of substrate (0.2 mmol) and
Pd/C (5 mg, 0.0048 mmol). The resulting mixture was then stirred at room temperature. The
reaction mixture was filtrated to remove Pd/C and cyanuric acid, and the filtrate was concentrated
in vacuo, the residue was directly subjected to the NMR analysis. The yield was determined by
comparing the integration of the methyl protons of acetonitrile and the anomeric proton of the
glycoside.

Reaction procedure using triethylsilane and palladium

Under argon atmosphere, nucleophile and triethylsilane (1.2 mmol) was added to the mixture of
substrate (0.2 mmol) and Pd/C (5 mg, 0.0048 mmol). The resulting mixture was then stirred at room
temperature. The reaction mixture was filtrated to remove Pd/C and cyanuric acid, and the filtrate
was concentrated in vacuo, the residue was directly subjected to the NMR analysis. The yield was
determined by comparing the integration of the methyl protons of acetonitrile and the anomeric
proton of the glycoside.

Methyl -D-melibioside (Entry 8)

1H NMR (500 MHz, D2O) : δ 4.98 (1H, d, H-1’, J=3.6 Hz), 4.82 (1H, d, H-1, J=3.8 Hz), 4.02-3.95 (3H,
m, H-4’, H-6b, H-5’), 3.90-3.85 (1H, m, H-3’), 3.83 (1H, d, H-2’, J=3.6 Hz), 3.81 (1H, d, H-5, J=3.6 Hz),
3.78-3.72 (3H, m, H-6’b, H-6a, H-6’a), 3.66 (1H, t, H-3), 3.60-3.55 (1H, m, H-2), 3.51 (1H, t, H-4), 3.42
(3H, s, OCH3)
13C NMR (126 MHz, D2O) : δ 99.4 (C-1), 98.1 (C-1’), 73.3 (C-3), 71.2 (C-2), 71.0 (C-5’), 70.1 (C-5),
69.5 (C-3’), 69.4 (C-4), 69.2 (C-4’), 68.4 (C-2’), 65.6 (C-6), 61.1 (C-6’), 55.2 (OCH3).

Ethyl -D-melibioside (Entry 9)

1H NMR (500 MHz, D2O) : δ 4.97 (1H, d, H-1’, J=3.3 Hz), 4.93 (1H, d, H-1, J=3.6 Hz), 4.02-3.92 (3H,
m, H-4’, H-6b, H-5’), 3.90-3.84 (2H, m, H-3’, H-5), 3.84-3.77 (2H, m, H-2’, OCH2CH3), 3.77-3.64 (4H,
m, H-6’b, H-6’a, H-6a, H-3), 3.61-3.46 (3H, m, OCH2CH3, H-2, H-4), 1.22 (3H, t, OCH2CH3)
13C NMR (126 MHz, D2O) : δ 99.4 (C-1’), 98.1 (C-1), 73.3 (C-3), 71.2 (C-2), 71.0 (C-5’), 70.1 (C-3’), 69.5
(C-4, C-5), 69.4 (C-4’), 69.2 (C-2’), 68.4 (C-6), 65.6 (OCH2CH3), 61.1 (C-6’), 14.1 (OCH2CH3).

2-propyl -D-melibioside (Entry 10)

1H NMR (500 MHz, D2O) : δ 5.04 (1H, d, H-1, J=3.9 Hz), 4.98 (1H, m, H-1’), 4.01-3.95 (4H, m, H-4’,
H-6b, H-5’, OCH(CH3)2), 3.95-3.90 (1H, m, H-5), 3.89-3.85 (1H, m, H-3’), 3.84-3.80 (1H, m, H-2’),
3.77-3.70 (3H, m, H-6’b, H-6’a, H-6a), 3.70-3.62 (1H, m, H-3), 3.56-3.52 (1H, m, H-2), 3.52-3.47 (1H,
m, H-4), 1.27-1.17 (6H, m, OCH(CH3)2)
13C NMR (126 MHz, D2O) : δ 98.0 (C-1’), 96.4 (C-1), 73.4 (C-3), 71.2 (C-2), 71.0 (OCH(CH3)2), 70.9
(C-5’), 70.3 (C-5), 69.6 (C-3’), 69.5 (C-4), 69.2 (C-4’), 68.4 (C-2’), 65.6 (C-6), 61.1 (C-6’), 22.4
3
(OCH(CH3)2).

Propargyl -D-melibioside (Entry 11)

1H NMR (500 MHz, D2O) : δ 5.09 (1H, d, H-1, J=3.8 Hz), 4.95 (1H, d, H-1’, J=3.7 Hz), 4.37-4.28 (2H,
m, OCH2C≡CH), 3.99-3.91 (3H, m, H-4’, H-5’, H-6b), 3.89-3.82 (2H, m, H-5, H-3’), 3.82-3.77 (1H, m,
H-2’), 3.75-3.69 (3H, m, H-6’b, H-6’a, H-6a), 3.69-3.64 (1H, m, H-3), 3.60-3.55 (1H, m, H-2), 3.54-3.46
(1H, m, H-4), 2.90-2.86 (1H, m, OCH2C≡CH);
13C NMR (126 MHz, D2O) : δ 98.0 (C-1’), 97.1 (C-1), 78.7 (OCH2C≡CH), 76.0 (OCH2C≡CH), 73.1
(C-3), 70.9 (C-5’), 70.9 (C-2), 70.7 (C-5), 69.4 (C-3’), 69.3 (C-4), 69.2 (C-4’), 68.4 (C-2’), 65.4 (C-6), 61.1
(C-6’), 54.9 (OCH2C≡CH).

Methyl -D-maltopentaoside (Entry 12)

1H NMR (500 MHz, D2O) : δ 5.39-5.34 (4H, m, H-1’, H-1’’, H-1’’’, H-1’’’’), 4.77 (1H, H-1, overlapping
with other peaks), 4.00-3.52 (30H, m, sugar-H), 3.38 (3H, s, OCH3)
13C NMR (126 MHz, D2O) : δ 99.7-99.1 (5C, C-1, C-1’, C-1’’, C-1’’’, C-1’’’’), 73.5-69.3 (sugar-C),
60.6-60.1 (5C, C-6, C-6’, C-6’’, C-6’’’, C-6’’’’), 55.0 (OCH3).

Propargyl -D-maltopentaoside (Entry 13)

1H NMR (500 MHz, D2O) : δ 5.37-5.33 (4H, m, H-1’, H-1’’, H-1’’’, H-1’’’’), 5.06 (1H, H-1, J=3.7 Hz),
4.31-4.29 (2H, m, OCH2C≡CH), 3.96-3.35 (30H, m, sugar-H), 2.87-2.86 (1H, m, OCH2C≡CH)
13C NMR (126 MHz, D2O) : δ 99.8-97.1 (5C, C-1, C-1’, C-1’’, C-1’’’, C-1’’’’), 81.9-69.3 (sugar-C,
OCH2C≡CH, OCH2C≡CH), 60.4-60.2 (5C, C-6, C-6’, C-6’’, C-6’’’, C-6’’’’), 54.9 (OCH2C≡CH).

4
 4,6-dibenzyloxy-1,3,5-triazin-2-yl glucoside (DBT--Glc) 2a
0.40 DBnT-Glc.001.001.1r.esp

0.35
OH OBn
O N
HO O N
HO
OH N
0.30
OBn

0.25

0.20

0.15

0.10

0.05

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0
Chemical Shift (ppm)
5
 4,6-dibenzyloxy-1,3,5-triazin-2-yl glucoside (DBT--Glc) 2a
DBnT-Glc.003.001.1r.esp
0.13

0.12

OH OBn
0.11 O N
HO O N
HO
OH N
0.10 OBn

0.09

0.08

0.07

0.06

0.05

0.04

0.03

0.02

0.01

170 160 150 140 130 120 110 100 90 80 70 60 50

Chemical Shift (ppm)
6
70 DBT-Mel.001.001.1r.esp
4,6-dibenzyloxy-1,3,5-triazin-2-yl melibioside (DBT--Mel) 2b
65

60

55
HO OH
O
50
HO
OH OBn
O
45 O N
HO O N
HO
OH N
40 OBn

35

30

25

20

15

10

05

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5

Chemical Shift (ppm)
7
1.0 CDBT-Mel.002.001.1r.esp
4,6-dibenzyloxy-1,3,5-triazin-2-yl melibioside (DBT--Mel) 2b

0.9

0.8
HO OH
O
HO
0.7 OH OBn
O
O N
HO O N
HO
OH N
0.6
OBn

0.5

0.4

0.3

0.2

0.1

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56
Chemical Shift (ppm)
8
 4,6-dibenzyloxy-1,3,5-triazin-2-yl maltopentaoside (DBT--Maltopenta) 2c
1.0 101209.DBT-Maltopentaoside.1r(1H).esp

0.9 OH
O
HO
HO OH
OH O
0.8 O
OH
HO
OH O
O
HO OH
0.7 OH
O
O
OH OBn
HO
OH O N
O O N
0.6 HO
OH N
OBn

0.5

0.4

0.3

0.2

0.1

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0
Chemical Shift (ppm)
9
0.70 101209.007.001.1r.esp
4,6-dibenzyloxy-1,3,5-triazin-2-yl maltopentaoside (DBT--Maltopenta) 2c
0.65
OH
0.60 O
HO
HO OH
OH O
0.55 O
OH
HO
OH O
O
0.50 HO OH
OH O
O OBn
HO OH
0.45 OH O N
O O N
HO
OH N
0.40 OBn

0.35

0.30

0.25

0.20

0.15

0.10

0.05

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56
Chemical Shift (ppm)
10
 Methyl glucoside (entry 1)
1.001.001.1r.esp
0.55

OH
0.50
O
HO
HO
OH
0.45 O

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2
Chemical Shift (ppm)
11
 Ethyl glucoside (entry 2)
0.70 DBnT-Glc_EtOH.001.001.1r.esp

0.65
OH
O
0.60 HO
HO
OH
O
0.55

0.50

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

Chemical Shift (ppm)
12
 Ethyl glucoside (entry 2)

1.0 DBnT-Glc_EtOH.002.001.1r.esp
OH
O
HO
0.9 HO
OH
O

0.8

0.7
Normalized Intensity

0.6

0.5

0.4

0.3

0.2

0.1

104 96 88 80 72 64 56 48 40 32 24 16 8
Chemical Shift (ppm)
13
 Octyl glucoside (entry 3)
1.0 DBT-Glc_Octyl.001.001.1r.esp

OH
0.9 O
HO
HO
OH
O
0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
Chemical Shift (ppm)
14
 Octyl glucoside (entry 3)
DBT-Glc_Octyl.002.001.1r.esp
0.55
OH
O
HO
0.50 HO
OH
O
0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

104 96 88 80 72 64 56 48 40 32 24 16 8
Chemical Shift (ppm)
15
0 DBnT-Glc_iPrOH.001.001.1r.esp
2-Propyl glucoside (entry 4)

5 OH
O
HO
HO
OH
O
0

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

Chemical Shift (ppm)
16
 2-Propyl glucoside (entry 4)
1.0 DBnT-Glc_iPrOH.002.001.1r.esp

0.9 OH
O
HO
HO
OH
0.8 O

0.7

0.6

0.5

0.4

0.3

0.2

0.1

104 96 88 80 72 64 56 48 40 32 24 16
Chemical Shift (ppm)
17
 Cyclohexyl glucoside (entry 5)
1.0 DBT-Glc_cycHex.001.001.1r.esp

0.9 OH
O
HO
HO
OH
0.8 O

0.7

0.6

0.5

0.4

0.3

0.2

0.1

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
Chemical Shift (ppm)
18
 Cyclohexyl glucoside (entry 5)
DBT-Glc_cycHex.002.001.1r.esp

0.30 OH
O
HO
HO
OH
O

0.25

0.20

0.15

0.10

0.05

104 96 88 80 72 64 56 48 40 32 24 16
Chemical Shift (ppm)
19
 Pentenyl glucoside (entry 6)
CDBT-Glc pentenol.001.001.1r.esp

OH
0.30 O
HO
HO
OH
O

0.25

0.20

0.15

0.10

0.05

6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
Chemical Shift (ppm)
20
 Pentenyl glucoside (entry 6)
0 CDBT-Glc pentenol.002.001.1r.esp

9 OH
O
HO
HO
OH
8 O

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

Chemical Shift (ppm)
21
 Propargyl glucoside (entry 7)
DBT-Glc_prop.001.001.1r.esp
0.55
OH
0.50 HO
O
HO
OH
O
0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

5.0 4.5 4.0 3.5 3.0

Chemical Shift (ppm)
22
 Propargyl glucoside (entry
DBT-Glc_prop.002.001.1r.esp 7)

0.25 OH
O
HO
HO
OH
O

0.20

0.15

0.10

0.05

136 128 120 112 104 96 88 80 72 64 56 48

Chemical Shift (ppm)
23
 Methyl melibioside
1.0 CDBT-Mel (entry
sov.001.001.1r.esp 8)

0.9

HO OH
0.8 O
HO
OH
O
O
0.7 HO
HO
OH
O

0.6

0.5

0.4

0.3

0.2

0.1

5.0 4.5 4.0 3.5

Chemical Shift (ppm)
24
 Methyl melibioside (entry 8)
1.0 CDBT-Mel sov.002.001.1r.esp

0.9
HO OH
O
0.8
HO
OH
O
O
0.7 HO
HO
OH
O

0.6

0.5

0.4

0.3

0.2

0.1

110 105 100 95 90 85 80 75 70 65 60 55 50 45 40

Chemical Shift (ppm)
25
 Mel-Et.001.001.1r.esp
16
Ethyl melibioside (entry 9)
15

14
HO OH
O
13
HO
OH
O
12 O
HO
HO
11 OH
O

10

09

08

07

06

05

04

03

02

01

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

Chemical Shift (ppm)
26
 Ethyl melibioside
1.0 CDBT-Mel (entry 9)
sov.002.001.1r.esp

0.9 HO OH
O
HO
OH
0.8 O
O
HO
HO
OH
0.7 O

0.6

0.5

0.4

0.3

0.2

0.1

100 95 90 85 80 75 70 65 60 55 50
Chemical Shift (ppm)
27
 CDBT-Mel
2-PropyliPrOH.001.001.1r.esp
melibioside (entry 10)
.09

.08 HO OH
O
HO
OH
O
.07 O
HO
HO
OH
O
.06

.05

.04

.03

.02

.01

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

Chemical Shift (ppm)
28
 2-PropyliPrOH.002.001.1r.esp
1.0 CDBT-Mel melibioside (entry 10)

0.9
HO OH
O
0.8
HO
OH
O
O
0.7 HO
HO
OH
O
0.6
1.0 CDBT-Mel iPrOH.002.001.1r.esp

0.5
0.9

0.8
0.4
0.7

0.3
0.6

0.5

0.2
0.4

0.3
0.1
0.2

0
0.1

-0.1
-0.1

104 96 88 80 72 64 56 48 40 32 24 16
Chemical Shift (ppm)
104 96 88 80 72 64 56 48 40 32 24 16
Chemical Shift (ppm)
29
 Propargyl melibioside (entry 11)
DBT-Mel propalgyl 3.001.001.1r.esp
0.16

0.15
HO OH
0.14
O
HO
0.13 OH
O
O
0.12 HO
HO
OH
0.11 O

0.10

0.09

0.08

0.07

0.06

0.05

0.04

0.03

0.02

0.01

5.0 4.5 4.0 3.5 3.0

Chemical Shift (ppm)
30
 Propargyl melibioside (entry 11)
1.0 DBT-Mel propalgyl 3.002.001.1r.esp

0.9 HO OH
O
HO
0.8 OH
O
O
HO
HO
OH
0.7 O

0.6

0.5

0.4

0.3

0.2

0.1

110 105 100 95 90 85 80 75 70 65 60 55 50 45 40

Chemical Shift (ppm)
31
 Methyl maltopentaoside (entry 12)
0.70 Maltopenta-Me.001.001.1r.esp

OH
0.65
O
HO
HO OH
0.60 OH
O
O
HO OH
OH O
0.55 O
HO OH
OH O
O
HO OH
0.50
OH O
O
HO
0.45 OH
O
Normalized Intensity

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

5.0 4.5 4.0 3.5

Chemical Shift (ppm)
32
 Methyl maltopentaoside (entry 12)
1.0 DBT-Maltopenta MeOH.002.001.1r.esp

OH
0.9 HO
O
HO OH
OH O
O
HO OH
0.8 OH O
O
HO OH
OH O
O
0.7 HO OH
OH O
O
HO
OH
0.6 O

0.5

0.4

0.3

0.2

0.1

105 100 95 90 85 80 75 70 65 60 55 50 45
Chemical Shift (ppm)
33
Propargyl -maltopentaoside (entry 13)

OH
O
HO
HO OH
OH O
O
HO OH
OH O
O
HO OH
OH O
O
HO OH
OH O
O
HO
OH
O

5.0 4.5 4.0 3.5 3.0 2.5

Chemical Shift (ppm)
34
 Propargyl -maltopentaoside (entry 13)
1.0 DBT-Maltopenta propalgyl.002.001.1r.esp
OH
O
0.9 HO
HO OH
OH O
O
HO OH
0.8 OH O
O
HO OH
OH O
O
HO OH
0.7 OH O
O
HO
OH
O
0.6
Normalized Intensity

0.5

0.4

0.3

0.2

0.1

110 105 100 95 90 85 80 75 70 65 60 55 50 45 40

Chemical Shift (ppm)
35