Sodium Azide → 8-Azido-2'-deoxyadenosine

HRID 2050603Notes

Reaction equation

Br[C:2]1[N:3]([C:12]2[N:13]=[CH:14][N:15]=[C:16]([NH2:19])[C:17]=2[N:18]=1)[C@@H:4]1[O:11][C@H:8]([CH2:9][OH:10])[C@@H:6]([OH:7])[CH2:5]1.[N-:20]=[N+:21]=[N-:22].[Na+]>CN(C=O)C>[N:20]([C:2]1[N:3]([C:12]2[N:13]=[CH:14][N:15]=[C:16]([NH2:19])[C:17]=2[N:18]=1)[C@@H:4]1[O:11][C@H:8]([CH2:9][OH:10])[C@@H:6]([OH:7])[CH2:5]1)=[N+:21]=[N-:22]

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of 8-bromo-2'-deoxyadenosine (0.403 g, 1.22 mmol) in DMF (25 ml) was added sodium azide (0.278 g, 4.27 mmol), and the mixture stirred at 90° C. for 2 h. The solvent was removed and the residue was purified on silica gel (10% methanol/chloroform) to give 0.325 g (91%) of 8-azido-2'-deoxyadenosine: 1H NMR (Me2SO-d6)δ2.17 (m, 2H), 3.59 (m, 2H), 3.82 (m, 1H), 4.42 (m, 1H), 5.25 (m, 2H), 6.11 (m, 1H), 7.24 (br.s, 2H), 8.07 (s, 1H); UV (H2O) λmax 282.5 nm; FTIF (KBr) 2155 cm-1. 8-Azido-2'-deoxyadenosine was silylated by Procedure A (77% yield) and then reduced, dideoxygenated, and converted to 8-amino-2',3'-dideoxyadenosine (VIII) using in sequence Procedure D (79%), Procedure E (77%), and Procedure F (81%): mp 177°-179° C., 13C NMR (Me2SO-d6) δ26.0, 29.0, 63.1, 79.5, 83.9, 117.1, 148.4, 148.9, 151.4, 152.3; 1H NMR (Me2SO-d6) 2.16 (m, 4H), 3.61 (m, 2H), 4.11 (m, 1H), 5.54 (m, 1H), 6.10 (m, 1H), 6.40 (br.s, 2H), 6.52 (br.s, 2H), 7.89 (s, 1H); UV (H2O) λmax 273.5 nm (λ13950); FAB HRMS obsd (M+ +H) 251.1266, calcd for C10H14N6O2 251.1257.

Workup

customThe solvent was removed
customthe residue was purified on silica gel (10% methanol/chloroform)

Sources & evidence

ORD record: ord-e610191e83b9417097ded1cff785ea94
Source dataset: uspto-grants-1991_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05013829

Reaction notes

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