ACCEPTED MANUSCRIPT
J2’,3’ = 7.9 Hz, 1H, H-2’), 5.56 (m, 2H, H-4’,3’), 5.23 (d, J1’’,2’’ = 4.4 Hz, 1H, H-1’’), 4.91 (d, J1’,2’ = 6.0 Hz,
1H, H-1’), 4.69 (d, 2JCHHPh, CHHPh = 10.0 Hz, 1H, CHHPh), 4.66 (d, 2JCHHPh, CHHPh = 10.0 Hz, 1H, CHHPh), 4.56
(d, 2JCHHPh, CHHPh = 15.2 Hz, 1H, CHHPh), 4.53 (d, 2JCHHPh, CHHPh = 15.2 Hz, 1H, CHHPh), 4.46 (d, 2JCHHPh, CHHPh
= 12.2 Hz, 1H, CHHPh), 4.40 (d, 2JCHHPh, CHHPh = 12.2 Hz, 1H, CHHPh), 4.27 (dd, J3’’,4’’ = 7.4 Hz, J4’’,5’’ = 3.7
2
Hz, 1H, H-4’’), 4.20 (dd, J4’,5a’ = 3.8 Hz, J5a’,5b’ = 12.8 Hz, 1H, H-5a’), 4.03-4.00 (m, 1H, H-2), 3.92 (dd,
J2,3a = 6.3, J3a,3b = 10.9, 1H, H-3a), 3.86-3.81 (m, 2H, H-3’’,3b), 3.77 (dd, J1’’,2’’ = 4.4 Hz, J2’’,3’’ = 6.5 Hz,
2
1H, H-2’’), 3.72 (dd, J4’,5b’ = 1.8 Hz, J5a’,5b’ = 12.8 Hz, 1H, H-5b’), 3.51 (d, J1,2 = 5.4 Hz, 2H, H-1), 3.36
(dd, J4’’,5’’ = 3.7 Hz, 2J5a’’,5b’’ = 3.7 Hz, 2H, H-5a’’,5b’’), 3.34-3.26 (m, 2H, H-4), 3.27 (t, J5,6 = 6.8 Hz, 2H, H-
6), 1.69-1.62 (m, 2H, H-5); 13C NMR (100.6 MHz, CDCl3): 165.7, 165.6, 165.3 (3 × C=O), 138.4, 138.1,
138.0, 133.3, 133.3, 129.9, 129.9, 129.5, 129.2, 128.5, 128.4, 128.4, 128.4, 128.4, 128.3, 128.1,
127.8, 127.7, 127.7, 127.6, 127.6, 127.6, 101.4 (C1’’), 100.5 (C1’), 81.8 (C4’’), 75.7 (C2), 75.6 (C3’’),
74.4 (CH2Ph), 72.4 (CH2Ph), 72.2 (CH2Ph), 71.5 (C1), 70.5 (C3’), 70.1 (C2’), 70.0 (C5’’), 67.0 (C3), 68.5
(C4’), 67.9 (C4), 62.2 (C5’), 48.4 (C6), 29.1 (C5); HRMS (ESI+) m/z calc. for C58H59N3O14Na+ 1044.3889
[M+Na]+ found 1044.3890 [M+Na]+.
4.18. General procedure for deprotection of compounds 27 and 28.
(2R)- or (2S)-3-(3-Azidopropoxy)-2-(2,3,5-tri-O-benzyl-α-ᴅ-ribofuranosyloxypropyl 2,3,4-tri-O-
benzoyl-α-ʟ-arabinopyranoside (27) or (28) respectively was dissolved in a mixture of MeOH (10 mL)
and EtOAc (5 mL) and hydrogenated over 10% Pd/C (5 mg) under a H2 at 50 °C for 24 hours. The
resulting mixture was filtered through Celite®, the filter was washed with additional MeOH (25 mL)
and the solvent was removed in vacuo. The residue was dissolved in a mixture of MeOH/H2O/Et3N
(5:2:1 mL) and stirred at room temperature overnight. The mixture was concentrated in vacuo and
the residue was passed through a short column of Dowex® 1X2-400 resin (OH- form) in water. The
sample was lyophilised to give target compounds 6 and 7.
(2R)-3-(3-Aminopropoxy)-2-(α-ᴅ-ribofuranosyloxy)propyl α-ʟ-arabinopyranoside (6) was prepared
from 27 (45 mg, 44 µmol) as a white powder (10.7 mg, 59%); [α]D +40.4 (c = 1.0, H2O); 1H NMR (400
MHz, D2O): 5.24 (d, J1’’,2’’ = 4.4 Hz, 1H, H-1’’), 4.29 (d, J1’,2’ = 7.7 Hz, 1H, H-1’); 4.07 (dd, J3’’,4’’ = 6.6 Hz,
J4’’,5a’’ = 3.7 Hz, 1H, H-4’’), 4.04-4.00 (m, 2H, H-4’,2’’), 3.95 (dd, J2’’,3’’ = 3.5 Hz , J3’’,4’’ = 6.6 Hz, 1H, H-3’’),
3.90-3.83 (m, 4H, H-3a, 2, 5a’), 3.75 (dd, J2,3b = 4.4 Hz, J3a,3b = 11.4 Hz, 1H, H-3b), 3.68 (dd, J4’’,5a’’ = 3.7
Hz, J5a’’,5b’’ = 12.4 Hz), 1H, H-5a’’), 3.63-3.46 (m, 8H, H-1,5b’’,3’,5’,4,2’), 2.60 (t, J5,6 = 6.9 Hz, 1H, H-6),
1.70-1.61 (m, 1H, H-5); 13C NMR (100.6 MHz, D2O): 103.4 (C1’), 101.9 (C1’’), 84.7 (C4’’) 75.7 (C4’),
72.3 (C3’), 71.3 (C2’’), 70.7 (C2’), 70.2 (C1), 69.6 (C3’’), 69.3 (C4), 69.1 (C3), 68.2 (C2), 66.2 (C5’), 61.5
(C5’’), 37.7 (C6), 31.4 (C5); HRMS (ESI+) m/z calc. for C16H31NO11Na+ 414.1970 [M+Na]+ found
414.1968 [M+Na]+
.
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