Syntheses of Novel Sulfated Glycans for Cell-Adhesion Interaction Studies

Abstract

Stereoselective syntheses of two 3-O-Gal sulfated trisaccharides GalNAcβ(1-4)[(3-SE)-Gal]β(1-3)GalNAcα-O-All and GalNAcβ(1-4)[(3-SE)-Gal]β(1-4)Glcβ-O-All were accomplished through the use of three novel glycosyl acceptors, namely, allyl 4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α-d-galactopyranoside, methyl 2,6-di-O-benzoyl-3-O-naphthylmethyl-α-d-galactopyranoside and allyl 6-O-acetyl-2-O-benzoyl-3-O-naphthylmethyl-β-d-galactopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-β-d-glucopyranoside. These sulfated trisaccharides were expected to act as potential reference compounds for human β4GalNAc transferase and can be effectively used as antigens when linked to KLH.

Key words

glycosylations - oligosaccharides - stereoselective synthesis - sulfated glycans - sulfotransferases

References and Notes

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18

Analytical Data for Compound 1
^¹H NMR (400 MHz, CD₃OD): δ = 1.97 (s, 3 H, NHCOCH ₃), 2.03 (s, 3 H, NHCOCH ₃), 3.93-3.41 (m, 16 H), 4.03-3.98 (m, 2 H), 4.11-4.09 (m, 1 H), 4.23-4.17 (m, 1 H), 4.39 (d, J = 7.6 Hz, 1 H, H-1′), 4.46-4.41 (m, 1 H), 4.63 (d, J = 8.4 Hz, 1 H, H-1′′), 5.17 (dd, ^³ J = 10.4 Hz, ^² J = 1.6 Hz, 1 H, OCH₂CH=CH _cis H _trans ), 5.32 (dd, ^³ J = 17.2 Hz, ^² J = 1.6 Hz, 1 H, OCH₂CH=CH _cis H _trans ), 5.99-5.89 (m, 1 H, OCH₂CH=CH₂) ppm. ^¹³C NMR (100 MHz, CD₃OD): δ = 22.9 (COCH₃), 23.2 (COCH₃), 55.5, 61.8, 62.8, 62.9, 69.4, 70.3, 72.4, 72.8, 72.9, 74.7, 74.8, 75.8, 77.0, 77.9, 78.5 (C-3), 78.9 (C-3′), 98.2, 104.6, 106.5 (C-1, C-1′, C-1′′), 117.8 (CH=CH₂), 135.7 (CH=CH₂), 174.2 (COCH₃), 175.4 (COCH₃) ppm. ESI-MS: m/z calcd for C₂₅H₄₁N₂NaO₁₉S: 728.2; found: 751.2 [M + Na]⁺.

20

Analytical Data for Compound 6
^¹H NMR (400 MHz, CD₃OD): δ = 2.06 (s, 3 H, NHCOCH ₃), 3.26 (m, 1 H), 3.91-3.46 (m, 14 H), 4.16-4.01 (m, 2 H), 4.36-4.28 (m, 4 H, H-1, J = 8.0 Hz, incorporated with other protons), 4.44 (d, J = 7.6 Hz, 1 H, H-1′), 4.61 (d, J = 8.4 Hz, 1 H, H-1′′), 5.16 (dd, ^³ J = 10.8 Hz, ^² J = 1.2 Hz, 1 H, OCH₂CH=CH _cis H _trans ), 5.32 (dd, ^³ J = 17.6 Hz, ^² J = 1.6 Hz,
1 H, OCH₂CH=CH _cis H _trans ), 5.99-5.93 (m, 1 H, OCH₂CH=CH₂) ppm. ^¹³C NMR (100 MHz, CD₃OD): δ = 23.5 (COCH₃), 54.2, 61.4, 61.9, 62.7, 69.8, 70.9, 71.3, 73.8, 74.9, 75.7, 76.4, 76.6, 76.7, 76.8, 81.0 (C-3), 81.1 (C-3′), 103.4, 104.9, 105.0 (C-1, C-1′, C-1′′), 117.6 (CH=CH₂), 135.8 (CH=CH₂), 174.9 (COCH₃) ppm. ESI-MS: m/z calcd for C₂₃H₃₈NNaO₁₉S: 687.2; found: 710.2 [M + Na]⁺.