S. C. Timmons, D. L. Jakeman / Carbohydrate Research 343 (2008) 865–874
873
salt) was obtained as a white solid in 30% yield by UV
spectroscopy (kmax 261 nm, e = 1.01 ꢁ 104 Mꢀ1 cmꢀ1).
The reported 1H NMR data are consistent with the
selected data reported by Barber and Behrman.45 1H
NMR (500 MHz, D2O, pH 6): d 7.99 (d, J5,6 8.0 Hz,
1H and 13C{1H} NMR data were consistent with that
of Auge and co-workers.46 31P{1H} NMR (202 MHz,
´
D2O, pH 6): d ꢀ11.2 (d, JP,P 20.2 Hz), ꢀ12.9 (d); tR
25 = 5.60 min (Method A); HRESIMSꢀ (m/z): calcd
for C15H23N2O16P2 549.0528, found 549.0503.
1H, H-6), 6.02 (m, 2H, H-10, H-5), 5.47 (dd, J1 ,P
00
7.5 Hz, J1 ;2 1:5 Hz, 1H, H-100), 4.41 (m, 2H,
00 00
4.2.18. ADP-a-L-arabinose (26). Following the proce-
dure used for the preparation of ADP-a-D-glucose
(20), a-L-arabinose-1-phosphate (15) (tributylammo-
nium salt (1.49 equiv), 102 mg, 0.200 mmol) was cou-
pled with AMP-N-methylimidazolide (18) (ꢂ0.10 mmol)
to prepare ADP-a-L-arabinose (26). After purification
as described for 20, ADP-a-L-arabinose (26, diammo-
nium salt) was obtained as a white solid in 35%
yield by UV spectroscopy (kmax 260 nm, e = 1.51 ꢁ
104 Mꢀ1 cmꢀ1). 1H NMR (500 MHz, D2O, pH 6): d
8.17 (s, 1H, H-8), 7.94 (s, 1H, H-2), 6.03 (d,
H-20, H-30), 4.33 (m, 1H, H-40), 4.25 (m, 2H, H-5a0,
H-5b0), 4.08 (m, 1H, H-200), 3.95 (dq, J4 ;5 9:5 Hz,
00 00
J5 ;6 6:5 Hz, 1H, H-500), 3.91 (dd, J2 ;3 3:5 Hz,
00 00
00 00
J3 ;4 10:0 Hz, 1H, H-300), 3.48 (dd, 1H, H-400), 1.33 (d,
00 00
3H, H3-600); 13C{1H} NMR (126 MHz, D2O, pH 6): d
167.5 (C-4), 152.9 (C-2), 141.5 (C-6), 102.8 (C-5), 96.4
(C-100), 88.4 (C-10), 83.2 (C-40), 73.8 (C-20), 72.1 (C-400),
70.5 (C-200), 70.4 (C-300), 69.7 (C-500), 69.6 (C-30), 65.0
(C-50), 16.8 (C-600); 31P{1H} NMR (202 MHz, D2O,
pH 6): d ꢀ11.5 (d, JP,P 20.4 Hz), ꢀ13.9 (d); tR
23 = 5.58 min (Method A); HRESIMSꢀ (m/z): calcd
for C15H23N2O16P2 549.0528, found 549.0485.
J1 ;2 6:0 Hz, 1H, H-10), 4.92 (dd, J1 ;P 7:5 Hz,
0
0
00
J1 ;2 8:0 Hz, 1H, H-100), 4.81 (dd, J2 ;3 5:5 Hz, 1H, H-
00 00
0
0
20), 4.66 (dd, J3 ;4 3:5 Hz, 1H, H-30), 4.47 (m, 1H, H-
0
0
4.2.16. ADP-b-L-fucose (24). Following the procedure
used for the preparation of ADP-a-D-glucose (20), b-L-
fucose-1-phosphate (10) (tributylammonium salt
(1.53 equiv), 106 mg, 0.200 mmol) was coupled with
AMP-N-methylimidazolide (18) (ꢂ0.10 mmol) to pre-
pare ADP-b-L-fucose (24). After purification as
described for 22, ADP-b-L-fucose (24, diammonium
salt) was obtained as a white solid in 28% yield by UV
spectroscopy (kmax 260 nm, e = 1.51 ꢁ 104 Mꢀ1 cmꢀ1).
1H NMR (500 MHz, D2O, pH 6): d 8.55 (s, 1H, H-8),
40), 4.32 (m, 2H, H-5a0, H-5b0), 4.04 (m, 1H, H-400),
4.03 (dd, J4 ;5a00 2:5 Hz, J5a00;5b 12:5 Hz, 1H, H-5a00),
00
00
3.83 (m, 2H, H-300, H-5b00), 3.79 (dd, J2 ;3 10:0 Hz,
00 00
1H, H-200); 13C{1H} NMR (126 MHz, D2O, pH 6): d
155.7 (C-6), 152.9 (C-2), 149.2 (C-4), 139.9 (C-8),
118.7 (C-5), 98.7 (C-100), 86.9 (C-10), 84.0 (C-40), 74.3
(C-20), 71.9 (C-200), 71.2 (C-300), 71.1 (C-30), 68.0 (C-400),
66.5 (C-500), 65.3 (C-50); 31P{1H} NMR (202 MHz,
D2O, pH 6): d ꢀ11.1 (d, JP,P 20.2 Hz), ꢀ13.0 (d); tR
26 = 5.34 min (Method A); HRESIMSꢀ (m/z): calcd
for C15H22N5O14P2 558.0644, found 558.0613.
8.30 (s, 1H, H-2), 6.18 (d, J1 ;2 6:0 Hz, 1H, H-10), 4.95
0
0
(dd, J1 ;P 8:0 Hz, J1 ;2 8:0 Hz, 1H, H-100), 4.82 (dd,
00
00 00
J2 ;3 5:5 Hz, 1H, H-20), 4.59 (dd, J3 ;4 3:5 Hz, 1H,
0
0
0
0
H-30), 4.44 (m, 1H, H-40), 4.26 (m, 2H, H-5a0, H-5b0),
4.2.19. UDP-a-L-arabinose (27). Following the proce-
dure used for the preparation of ADP-a-D-glucose
(20), a-L-arabinose-1-phosphate (15) (tributylammoni-
um salt (1.49 equiv), 102 mg, 0.200 mmol) was coupled
with UMP-N-methylimidazolide (19) (ꢂ0.10 mmol) to
prepare UDP-a-L-arabinose (27). After purification as
described for 20, UDP-a-L-arabinose (27, diammonium
salt) was obtained as a white solid in 32% yield by UV
spectroscopy (kmax 261 nm, e = 1.01 ꢁ 104 Mꢀ1 cmꢀ1).
1H, 13C{1H}, and 31P{1H} NMR data were consistent
with that of Ernst and Klaffke.19 tR 27 = 5.37 min
(Method A); HRESIMSꢀ (m/z): calcd for C14H21N2-
O16P2 535.0372, found 535.0322.
3.79 (br q, J5 ;6 6:5 Hz, 1H, H-500), 3.74 (br d,
00 00
J3 ;4 3:0 Hz, 1H, H-400), 3.68 (dd, J2 ;3 10:0 Hz, 1H,
00 00
00 00
H-300), 3.59 (dd, J1 ;2 7:5 Hz, 1H, H-200), 1.25 (d, 3H,
00 00
H3-600); 13C{1H} NMR (126 MHz, D2O, pH 6): d
155.7 (C-6), 153.0 (C-2), 149.3 (C-4), 139.9 (C-8),
118.7 (C-5), 98.4 (C-100), 86.8 (C-10), 84.0 (C-40), 74.3
(C-20), 72.5 (C-300), 71.5 (C-500), 71.2 (C-400), 71.1
(C-200), 70.5 (C-30), 65.3 (C-50), 15.4 (C-600); 31P{1H}
NMR (202 MHz, D2O, pH 6): d ꢀ11.1 (d, JP,P
20.8 Hz), ꢀ12.9 (d); tR 24 = 5.84 min (Method A);
HRESIMSꢀ (m/z): calcd for C16H24N5O14P2 572.0800,
found 572.0794.
4.2.17. UDP-b-L-fucose (25). Following the procedure
used for the preparation of ADP-a-D-glucose (20), b-L-
fucose-1-phosphate (10) (tributylammonium salt
(1.53 equiv), 106 mg, 0.200 mmol) was coupled with
UMP-N-methylimidazolide (19) (ꢂ0.10 mmol) to pre-
pare UDP-b-L-fucose (25). After purification as
described for 22, UDP-b-L-fucose (25, diammonium
salt) was obtained as a white solid in 26% yield by UV
spectroscopy (kmax 261 nm, e = 1.01 ꢁ 104 Mꢀ1 cmꢀ1).
Acknowledgments
This work was supported by a grant from the Canadian
Institutes of Health Research. We thank Professor Ben
G. Davis (Department of Chemistry, University of
Oxford) and Samy Mohamady (Tanta University,
Egypt) for helpful discussions.