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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+
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S7
2,5-Anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (10)
10
O
OH N3
OMe
OMe
HO
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S8
2,5-Anhydro-3-azido-3-deoxy-aldehydo-D-altrose dimethylacetal (10)
10
O
OH N3
OMe
OMe
HO
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S11
4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altronic acid (12)
O
AcO N3
OH
O
AcO
12
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S12
4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altronic acid (12)
O
AcO N3
OH
O
AcO
12
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S15
2,5-Anhydro-3-azido-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (14)
O
HO N3
OMeBnO
14
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S16
2,5-Anhydro-3-azido-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (14)
O
HO N3
OMeBnO
14
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S18
2,5-Anhydro-3-amino-6-O-benzyl-3-deoxy-1-O-methyl-D-altritol (15)
O
HO NH2
OMeBnO
15
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S21
4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altrose (17)
O
AcO N3
H
O
AcO
17
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S22
4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altrose (17)
O
AcO N3
H
O
AcO
17
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S23
4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altritol (18)
18
O
AcO N3
OHAcO
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S24
4,6-Di-O-acetyl-2,5-anhydro-3-azido-3-deoxy-D-altritol (18)
18
O
AcO N3
OHAcO
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S28
2030405060708090100110120130140150160170180190200 ppm
Methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranoside (24)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S30
2030405060708090100110120130140150160170180190 ppm
Ethyl (methyl 3-azido-2-O-benzoyl-3-deoxy-α-D-allopyranosid)uronyl glycinate (26)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S32
2030405060708090100110120130140150160170180190 ppm
Methyl (methyl 3-azido-2-O-benzoyl-3-deoxy--D-allopyranosid)uronate (28)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012