1  

Supporting Information

Synthesis of a tetrasaccharide and its glycoconjugate corresponding to the capsular polysaccharide of Neisseria meningitidis serogroup X and its immunochemical studies

Kishore R. Harale,1 Nilesh B. Dumare,1 Deepti Singh,1Anup Kumar Misra,2 Manoj Kumar Chhikara1*

1MSD Wellcome Trust Hilleman Laboratories Pvt. Ltd., 2nd Floor, Nanotechnology Building, Jamia Hamdard, Hamdard Nagar, New Delhi 110062,

India; E-mail: manoj.kumar@hillemanlabs.org 2Bose Institute, Division of Molecular Medicine, P-1/12, C.I.T. Scheme VII M, Kolkata

700054, India

Index

Subject Page No.

1D and 2D NMR spectra of compounds 2, 4, 7-11 and 1 2-19

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

2  

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

10

.63

3.0

4

7.7

4

3.2

0

1.0

71

.00

2.2

01

.07

1.0

5

1.0

0

1.0

0

0.5

0

2.9

88

.05

0.4

9

1.3

5

1H and 13C NMR spectra of 4-O-acetyl-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl hydrogen phosphonate triethylammonium salt (2) (CDCl3).

3  

1H and13C NMR spectra of 6-(N-benzyloxycarbonyl)aminohexyl 2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside (4) (CDCl3).

4  

1H and 13C NMR spectra of 6-(N-benzyloxycarbonyl)aminohexyl O-(4-O-acetyl-2-azido-3,6-

di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, triethylammonium salt (7) (CDCl3).

O

N3

AcOBnO

OBn

O P

O

O

O

O

N3

OBnO

OBn

5NHCbz7

Et3NH

O

N3

AcOBnO

OBn

O P

O

O

O

O

N3

OBnO

OBn

5NHCbz7

Et3NH

5  

2D COSY and 2D TOCSY NMR spectra (selected regions) of 6-(N-benzyloxycarbonyl) aminohexyl O-(4-O-acetyl-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, triethylammonium salt (7) (CDCl3).

O

N3

AcOBnO

OBn

O P

O

O

O

O

N3

OBnO

OBn

5NHCbz7

Et3NH

6  

2D HSQC and 2D HMBC NMR spectra (selected regions) of 6-(N-benzyloxycarbonyl)aminohexyl O-(4-O-acetyl-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-

glucopyranosyl phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, triethylammonium salt (7) (CDCl3).

O

N3

AcOBnO

OBn

O P

O

O

O

O

N3

OBnO

OBn

5NHCbz7

Et3NH

O

N3

AcOBnO

OBn

O P

O

O

O

O

N3

OBnO

OBn

5NHCbz7

Et3NH

7  

1H and 13C NMR spectra of 6-(N-benzyloxycarbonyl)aminohexyl O-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, triethylammonium salt (8) (CDCl3).

8  

2D COSY and 2D HSQC NMR spectra (selected regions) of 6-(N-benzyloxycarbonyl)aminohexyl O-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, triethylammonium salt (8) (CDCl3).

9  

1H and 13C NMR spectra of 6-(N-benzyloxycarbonyl)aminohexyl O-(4-O-acetyl-2-azido-3,6-

di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-

deoxy-α-D-glucopyranosyl phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, bis-triethylammonium salt (9) (CDCl3).

O

N3

BnO

OBn

O P

O

O

O

O

N3

OBnO

OBn

5NHCbz

9 Et3NH

O

N3

AcOBnO

OBn

O P

O

OO

Et3NH

O

N3

BnO

OBn

O P

O

O

O

O

N3

OBnO

OBn

5NHCbz

9 Et3NH

O

N3

AcOBnO

OBn

O P

O

OO

Et3NH

10  

2D COSY and 2D HSQC NMR spectra (selected regions) of 6-(N-benzyloxycarbonyl)aminohexyl O-(4-O-acetyl-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-

glucopyranosyl phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, bis-triethylammonium salt (9) (CDCl3).

11  

1H and 13C NMR spectra of 6-(N-benzyloxycarbonyl)aminohexyl O-(2-azido-3,6-di-O-benzyl-

2-deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-

glucopyranosyl phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, bis-triethylammonium salt (10) (CDCl3).

12  

2D COSY and 2D HSQC NMR spectra (selected regions) of 6-(N-benzyloxycarbonyl)aminohexyl O-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-

(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, bis-triethylammonium salt (10) (CDCl3).

13  

1H and 13C NMR spectra of 6-(N-benzyloxycarbonyl)aminohexyl O-(4-O-acetyl-2-azido-3,6-

di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-

deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-

glucopyranosyl phosphate)-(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, tris-triethylammonium salt (11) (CDCl3).

14  

2D COSY and 2D TOCSY NMR spectra (selected regions) of 6-(N-benzyloxycarbonyl)aminohexyl O-(4-O-acetyl-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-

glucopyranosyl phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-

(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, tris-triethylammonium salt (11) (CDCl3).

15  

2D HSQC and 2D HMBC NMR spectra (selected regions) of 6-(N-benzyloxycarbonyl)aminohexyl O-(4-O-acetyl-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-(2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyl phosphate)-

(14)-2-azido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside, tris-triethylammonium salt (11) (CDCl3).

16  

1H and 13C NMR spectra of 6-aminohexyl O-(2-acetamido-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-(2-acetamido-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-

acetamido-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-2-acetamido-2-deoxy-α-D-glucopyranoside, trisodium salt (1) (D2O).

17  

2D COSY and TOCSY NMR spectra (selected regions) of 6-aminohexyl O-(2-acetamido-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-acetamido-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-(2-acetamido-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-2-acetamido-2-deoxy-α-D-glucopyranoside, trisodium salt (1) (D2O).

18  

2D HSQC and HMBC NMR spectra (selected regions) of 6-aminohexyl O-(2-acetamido-2-

deoxy-α-D-glucopyranosyl phosphate)-(14)-(2-acetamido-2-deoxy-α-D-glucopyranosyl

phosphate)-(14)-(2-acetamido-2-deoxy-α-D-glucopyranosyl phosphate)-(14)-2-acetamido-2-deoxy-α-D-glucopyranoside, trisodium salt (1) (D2O).