Tetrabutylammonium Fluoride → 2',3'-Didehydro-2',3'-dideoxyadenosine

HRID 2209753Notes

Reaction equation

HRID 2209753 reaction equation
[Si]([O:8][CH2:9][C@H:10]1[O:14][C@@H:13]([N:15]2[C:24]3[N:23]=[CH:22][N:21]=[C:19]([NH2:20])[C:18]=3[N:17]=[CH:16]2)[CH:12]=[CH:11]1)(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1>[C@@H:13]1([N:15]2[C:24]3[N:23]=[CH:22][N:21]=[C:19]([NH2:20])[C:18]=3[N:17]=[CH:16]2)[O:14][C@H:10]([CH2:9][OH:8])[CH:11]=[CH:12]1

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 113938955'-O-tert-butyldimethylsilyl-2',3'-didehydro-2',3'-dideoxyadenosine

Product 1

HCID 649752',3'-Didehydro-2',3'-dideoxyadenosineYield 86.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 16 (3.79 g, 10.92 mmol) in dry THF (40 mL), cooled in an ice-bath, was added 22 ml of a 1M solution of tetra-n-butylammonium flouride in THF (22 mL, 22.0 mmol). The mixture was stirred for 40 minutes at room temperature and concentrated. The resulting yellow syrupy residue was purified by chromatography on a silica gel column using a gradient of 3-5% methanol in CHCl3. Evaporation of the appropriate fractions yielded 2.21 g (86%) of 7: mp 184°-186° C. (methanol); 1H NMR (DMSO-d6) δ 3.59 (2H, dd, J=4.1 Hz, 5.27 Hz, 5'-H), 4.80-5.10 (2H, m, 4'-H and OH), 6.14 (1H, ddd, J=1.46 Hz, 1.76 Hz, 5.86 Hz, 2'-H), 6.47 (1H, ddd, J=1.46 Hz, 1.76 Hz, 5.87 Hz, 3'-H), 6.94 (1H, m, 1'-H), 7.25 (2H, br s, NH2), 8.157 (1H, s, 8-H), 8.167 (1H, s, 2-H).

Workup

  1. concentrationconcentrated
  2. customThe resulting yellow syrupy residue was purified by chromatography on a silica gel column
  3. customEvaporation of the appropriate fractions

Sources & evidence

ORD record
ord-44baa4cc5bd14eb6929a31112a71130f
Source dataset
uspto-grants-1995_10
Patent number
US05455339

Reaction notes

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