synthesis of cyclically constrained sugar derived alpha ... · s1 synthesis of cyclically...

S1

Synthesis of cyclically constrained sugar derived /- and /-peptides

Antonio Franconetti, Sorel Jatunov, Pastora Borrachero, Manuel Gómez-Guillén, and

Francisca Cabrera-Escribano*

Departamento de Química Orgánica, Facultad de Química, Universidad de Sevilla, C/ Profesor

García González 1, 41012 Sevilla, Spain, Tel: +34954556868, Fax: +34954624960

E-mail: [email protected]

SUPPORTING INFORMATION

CONTENTS Page

(1R and 1S)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-

D-altritol (9a, 9b), 1H NMR S2

(1R)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-

D-altritol (9a), 1H NMR and

13C NMR S3

(1S)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-

-altritol (9b), 1H NMR and

13C NMR S5

2,5-Anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (10), 1H NMR and

13C NMR S7

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (11), 1H NMR

and 13

C NMR S9

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altronic acid (12), 1H NMR and

13C NMR S11

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-N-(ethoxycarbonyl-methyl)-

α-D-altruronamide (13), 1H NMR and

13C NMR S13

2,5-Anhydro-3-azido-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (14), 1H NMR and

13C NMR S15

2,5-Anhydro-3-amino-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (15), 1H NMR and

13C NMR S17

2,5-Anhydro-3-N-(tercbutoxycarbonylamino-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (16), 1H NMR and

13C NMR S19

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altrose (17), 1H NMR and

13C NMR S21

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altritol (18), 1H NMR and

13C NMR S23

Methyl 3-azido-2,4di-O-acetyl-3-deoxy-α-D-allopyranosiduronic acid (21), 1H NMR and

13C NMR S25

Methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranoside (24), 1H NMR and

13C NMR S27

Ethyl [methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranosiduronyl]-glycinate (26), 1H NMR and

13C NMR S29

Methyl (methyl 3-azido-2-O-benzoyl-3-deoxy--D-allopyranosid) uronate (28), 1H NMR and

13C NMR S31

Methyl [methyl 2-O-benzoyl-3-(N-tert-butoxycarbonyl-glycylamido)-3-deoxy-

-D-allopyranosid]uronate (30), 1H NMR and

13C NMR S33

Ethyl [methyl 2-O-benzoyl-3-(N-tert-butoxycarbonyl-glycylamido)-3-deoxy-

α-D-allopyranosid]uronyl-glycinate (31), 1H NMR and

13C NMR S35

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

S2

(1R and 1S)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-D-altritol (9a,b)

9a,b

O

O

O

N3Ph

F

HMeO(1/3.3)

R

O

O

O

N3Ph

OMe

HF

S+


S3

(1R)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-D-altritol (9a)

9a

O

O

O

N3Ph

F

HMeO

R


S4

(1R)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-D-altritol (9a)

9a

O

O

O

N3Ph

F

HMeO

R


S5

(1S)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-D-altritol (9b)

9b

O

O

O

N3Ph

OMe

HF

S


S6

(1S)-2,5-Anhydro-3-azido-4,6-O-benzylidene-3-deoxy-1-fluoro-1-O-methyl-D-altritol (9b)

9b

O

O

O

N3Ph

OMe

HF

S


S7

2,5-Anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (10)

10

O

OH N3

OMe

OMe

HO


S8

2,5-Anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (10)

10

O

OH N3

OMe

OMe

HO


S9

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (11)

11

O

AcO N3

OMe

OMe

AcO


S10

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (11)

11

O

AcO N3

OMe

OMe

AcO


S11

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altronic acid (12)

O

AcO N3

OH

O

AcO

12


S12

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altronic acid (12)

O

AcO N3

OH

O

AcO

12


S13

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-N-(ethoxycarbonylmethyl)-α-D-altruronamide (13)

O

AcO N3

AcO

O

HN

OEt

O

13


S14

4,6- 4,6-di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-N-(ethoxycarbonylmethyl)-α-D-altruronamide (13)

O

AcO N3

AcO

O

HN

OEt

O

13

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-N-(ethoxycarbonylmethyl)-α-D-altruronamide (13)


S15

2,5-Anhydro-3-azido-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (14)

O

HO N3

OMeBnO

14


S16

2,5-Anhydro-3-azido-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (14)

O

HO N3

OMeBnO

14


S17

2,5-Anhydro-3-amino-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (15)

O

HO NH2

OMeBnO

15

O

HO NH2

OMeBnO

15


S18

2,5-Anhydro-3-amino-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (15)

O

HO NH2

OMeBnO

15


S19

2,5-Anhydro-3--(N-tert-butoxycarbonyl-glycylamido)-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (16)

O

HOHN

OMe

NH

O

O

O

BnO

16


S20

2,5-Anhydro-3-(N-tert-butoxycarbonyl-glycylamido)-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (16)

O

HOHN

OMe

NH

O

O

O

BnO

16


S21

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altrose (17)

O

AcO N3

H

O

AcO

17


S22

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altrose (17)

O

AcO N3

H

O

AcO

17


S23

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altritol (18)

18

O

AcO N3

OHAcO


S24

4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altritol (18)

18

O

AcO N3

OHAcO


S25

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

3.1

53

.21

3.0

0

1.2

3

1.0

9

2.0

9

1.1

3

4.85.05.2 ppm

Methyl 3-azido-2,4di-O-acetyl-3-deoxy-α-D-allopyranosiduronic acid (21)


S26

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

170172 ppm

Methyl 3-azido-2,4di-O-acetyl-3-deoxy-α-D-allopyranosiduronic acid (21)


S27

1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0 ppm

3.0

0

3.9

4

1.0

3

0.9

8

1.0

2

1.9

80

.94

1.8

1

Methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranoside (24)


S28

2030405060708090100110120130140150160170180190200 ppm

Methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranoside (24)


S29

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0 ppm

3.5

7

3.0

0

1.0

02

.08

2.6

81

.01

1.0

0

1.8

6

0.8

6

2.1

41

.04

2.0

1

4.24.4 ppm

1.0

0

2.0

8

2.6

8

1.0

1

1.0

0

Ethyl (methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranosid)uronyl glycinate (26)


S30

2030405060708090100110120130140150160170180190 ppm

Ethyl (methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranosid)uronyl glycinate (26)


S31

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm

3.1

9

3.0

0

1.1

1

1.9

8

0.9

91

.00

2.2

11

.09

2.0

9

Methyl (methyl 3-azido-2-O-benzoyl-3-deoxy--D-allopyranosid) uronate (28)


S32

2030405060708090100110120130140150160170180190 ppm

Methyl (methyl 3-azido-2-O-benzoyl-3-deoxy--D-allopyranosid)uronate (28)


S33

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm

9.4

1

2.9

51

.42

3.0

41

.27

1.3

81

.08

1.0

71

.05

1.0

11

.00

2.1

81

.09

0.8

4

2.0

2

5.05.2 ppm

Methyl [methyl 2-O-benzoyl-3-(N-tert-butoxycarbonyl-glycylamido)-3-deoxy--D-allopyranosid]uronate (30)


S34

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Methyl [methyl 2-O-benzoyl-3-(N-tert-butoxycarbonyl-glycylamido)-3-deoxy--D-allopyranosid]uronate (30)


S35

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

3.7

19

.08

3.2

5

1.0

7

2.0

62

.46

3.3

5

1.0

5

2.0

4

1.0

0

0.7

5

2.2

01

.99

2.0

3

Ethyl [methyl 2-O-benzoyl-3-(N-tert-butoxycarbonyl-glycylamido)-3-deoxy-α-D-allopyranosid]uronyl-glycinate (31)


S36

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Ethyl [methyl 2-O-benzoyl-3-(N-tert-butoxycarbonyl-glycylamido)-3-deoxy-α-D-allopyranosid]uronyl-glycinate (31)


synthesis of cyclically constrained sugar derived alpha ... · s1 synthesis of cyclically...

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