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31P NMR (162.01 MHz, CDCl3):d ¼ 23.65. 13C NMR (100.57 MHz, CDCl3):
d ¼ 170.53, 170.04, 169.44, 169.27 (4 CH3CO), 83.41 (d, JC-P ¼ 3.8 Hz, C-1),
76.50 (C-5), 73.92 (C-3), 70.80 (C-2), 68.14 (C-4), 64.49, 64.24 (2d,
JC-P ¼ 5.3 Hz, 2 PCH2CH3), 62.11 (C-6), 21.11, 21.11, 21.09, 20.97 (4 CH3CO),
16.46, 16.28 (2 d, JC-P ¼ 7.7 Hz, CH3CH2P). Anal. Calcd for C18H29O12PS: C,
43.20; H, 5.84. Found: C, 43.22; H, 5.81.
2,3,4,6-Tetra-O-acetyl-b-D-mannosyl phophorothioate 3. [a]2D0 þ 58.88
(c 0.6, CHCl3). 1H NMR (400 MHz, CDCl3): d ¼ 5.75 (dd, 1 H, J ¼ 1.6 Hz,
JH-P ¼ 12.4 Hz, H1), 5.40 (dd, 1 H, J ¼ 2.9, 1.6 Hz, H2), 5.34 (t, 1 H,
J ¼ 9.9 Hz, H4), 5.24 (dd, 1 H, J ¼ 9.9, 2.9 Hz, H3), 4.22–4.14 (m, 5 H, H-6a,
H5, PCH2CH3), 4.10 (dd, 1 H, J ¼ 12.3, 2.2 Hz, H6b), 2.17, 2.09, 2.07, 2.01
(4s, 12 H, CH3CO), 1.38 (t, 6 H, J ¼ 7.1 Hz, CH3CH2P). 31P NMR
(162.01 MHz, CDCl3): d ¼ 23.34. 13C NMR (100.57 MHz, CDCl3): d ¼ 170.62,
169.95, 169.85, 169.66 (4 CH3CO), 83.51 (d, JC-P ¼ 3.1 Hz, C-1), 71.90
(d, JC-P ¼ 9.2 Hz, C-2), 71.51 (C-5), 69.16 (C-3), 66.01 (C-4), 64.74, 64.47 (2d,
JC-P ¼ 5.3 Hz, PCH2CH3), 62.54 (C-6), 21.31, 21.17, 21.14, 21.07 (4 CH3CO),
16.52, 16.44 (CH3CH2P). Anal. Calcd for C18H29O12PS: C, 43.20; H, 5.84.
Found: C, 43.24; H, 5.85.
2,3,4,6-Tetra-O-acetyl-b-D-galactosyl phosphorothioate 4. [a]2D0 þ 26.48 (c
1
1, CHCl3). H NMR (400 MHz, CDCl3): d ¼ 5.42 (dd, 1 H, J ¼ 3.4, 1.0 Hz, H4),
5.27 (t, 1 H, J ¼ 10.0 Hz, H2), 5.03 (dd, 1 H, J ¼ 10.0, 1.0 Hz, H3), 5.02 (t, 1 H,
J ¼ 10.0 Hz, JH-P ¼ 16.3 Hz, H1), 4.22–4.00 (m, 7 H, H5, H6a, H6b,
PCH2CH3), 2.09, 2.01, 1.97, 1.91 (4s, 12 H, CH3CO), 1.32–1.28 (m, 6 H,
CH3CH2P). 31P NMR (162.01 MHz, CDCl3): d ¼ 24.03. 13C NMR (100.57 MHz,
CDCl3): d ¼ 170.40, 170.22, 169.94, 169.51 (4 CH3CO), 84.04 (d, JC-
¼ 3.8 Hz, C-1), 75.30 (C-5), 71.96 (C-3), 68.10 (d, JC-P ¼ 10.0 Hz, C-2), 67.47
P
(C-4), 64.49, 64.22 (2d, JC-P ¼ 5.4 Hz, PCH2CH3), 61.77 (C-6), 21.16, 21.11,
21.09, 20.99 (4 CH3CO), 16.51, 16.37 (CH3CH2P). Anal. Calcd for
C18H29O12PS: C, 43.20; H, 5.84. Found: C, 43.18; H, 5.82.
2,3,4-Tri-O-acetyl-a,b-L-rhamnosyl phosphorothioate 5. 5a 1H NMR
(400 MHz, CDCl3): d ¼ 5.60 (dd, 1 H, J ¼ 1.7 Hz, JH-P ¼ 12.2 Hz, H1), 5.32
(dd, 1 H, J ¼ 3.2, 1.7, Hz, H2), 5.15 (ddd, 1 H, J ¼ 9.8, 3.2 Hz, JH-P ¼ 1.3 Hz,
H3), 5.04 (t, 1 H, J ¼ 9.8 Hz, H4), 4.20–4.04 (m, 4 H PCH2CH3), 4.02–3.98
(m, 1 H, H5), 2.13, 2.09, 2.00 (3s, 9 H, CH3CO), 1.32–1.27 (m, 6 H,
CH3CH2P), 1.20–1.17 (m, 6 H, H-6). 31P NMR (162.01 MHz, CDCl3):
1
d ¼ 23.71. 5b H NMR (400 MHz, CDCl3): d ¼ 5.44 (d, 1 H, J ¼ 1.7 Hz, H2),
5.18 (dd, 1 H, J ¼ 1.7 Hz JH-P ¼ 12.4 Hz H1), 5.01–5.00 (m, 2 H, H3, H4)
4.20–4.04 (m, 4 H, PCH2CH3), 3.59–3.55 (m, 1H, H5), 1.98, 1.93, 1.91 (3s,
9 H, CH3CO), 1.32–1.27 (m, 6 H, CH3CH2P), 1.20–1.17 (m, 3 H, H6).
31P NMR (162.01 MHz, CDCl3 d ¼ 24.03. 13C NMR 5a 1 5b (100.57 MHz,