Bromotrimethylsilane → (E)-9-(2-hydroxymethyl-4-phosphonobut-3-enyl)adenine
Reaction equation
[OH:1][CH2:2][CH:3](/[CH:15]=[CH:16]/[P:17]([O:23]C(C)C)([O:19]C(C)C)=[O:18])[CH2:4][N:5]1[CH:13]=[N:12][C:11]2[C:6]1=[N:7][CH:8]=[N:9][C:10]=2[NH2:14].Br[Si](C)(C)C>CN(C)C=O>[OH:1][CH2:2][CH:3](/[CH:15]=[CH:16]/[P:17]([OH:19])([OH:23])=[O:18])[CH2:4][N:5]1[CH:13]=[N:12][C:11]2[C:6]1=[N:7][CH:8]=[N:9][C:10]=2[NH2:14]Participants
Procedure
A solution of (E)-9-[2-hydroxymethyl-4-(diisopropoxyphosphoryl)but-3-enyl]adenine (107 mg, 280 μmol) and bromotrimethylsilane (0.86 g, 5.61 mmol) in N,N-dimethylformamide (5 ml) was stirred at room temperature under dry nitrogen for 18 h. The solvent was removed and the residue azetroped with methanol (×3). The residue was purified by column chromatography on reverse phase silica gel eluting with water to give (E)-9-(2-hydroxymethyl-4-phosphonobut-3-enyl)adenine as a white solid (34 mg, 40%), m.p. >300° C.; λmax (MeOH) 262 (10,704)nm; υmax (KBr) 3435, 1695, 1640, 1415, 1263, 1229 and 1030 cm-1 ; δH [(CD3)2SO/D2O] 2.73 (1H, m, CH), 3.37 (2H, d, J 6 Hz, CH2O), 4.13 (1H, dd, J 7 Hz and 14 Hz, CH2N), 4.30 (1H, dd, J 7 Hz and 14 Hz, CH2N), 5.65 (1H, pseudo-t, J 17 Hz, PCH=CH), 6.06 (1H, ddd, J 8Hz, 19 Hz, PCH=CH), 8.10 (1H, s, H-2/H-8), 8.17 (1H, s, H-2/H-8); FABMS (thioglycerol) 300 (MH+) (Found: C, 37.83; H, 4.83; N, 21.75%. C10H14N5O4P.H2O requires C, 37.86; H, 5.08; N, 22.07%).
Workup
- customThe solvent was removed
- customThe residue was purified by column chromatography on reverse phase silica gel eluting with water
Sources & evidence
- ORD record
- ord-f36e13c4651e4101a6662458108b6789
- Source dataset
- uspto-grants-1994_10
- Patent number
- US05356886
Reaction notes
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