Potassium sodium tartarate → HCID 52920495, compound

HRID 2410215Notes

Reaction equation

HRID 2410215 reaction equation
[NH2:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[C@@H:11]1[C:15](=[CH2:16])[C@H:14]([CH2:17][OH:18])[C@@H:13]([OH:19])[C@@H:12]1[F:20].[C:21]([CH:24]([CH:26]([C:28]([O-:30])=O)[OH:27])[OH:25])([O-])=[O:22].[Na+].[K+]>C(Cl)Cl.C(O)(C)C.C(Cl)(Cl)Cl>[C@@H:11]1([N:6]2[C:7]3[N:8]=[CH:9][N:10]=[C:2]([NH2:1])[C:3]=3[N:4]=[CH:5]2)[O:27][C@H:26]([CH2:28][OH:30])[C@@H:24]([OH:25])[C@H:21]1[OH:22].[NH2:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[C@@H:11]1[C:15](=[CH2:16])[C@H:14]([CH2:17][OH:18])[C@@H:13]([OH:19])[C@@H:12]1[F:20]

Participants

6

Reactant 2

HCID 9855836Potassium sodium tartarateHCID 52920495HCID 52920495, compound

Product 2

HCID 60961AdenosineHCID 52920495HCID 52920495, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21906603Chloroform isopropyl alcoholSolvent

Procedure

(+)-(1R,2R,3R,5R)-3-(6-amino-9H-9-purinyl)-2-fluoro-5-(hydroxymethyl)-4-methylenecyclopentan-1-ol (15) Diisobutylaluminum hydride (DIBAL-H, 1.6 mL, 1.0 M in toluene) was added slowly into the solution of compound 14 (160.0 mg, 0.33 mmol) in anhydrous CH2Cl2 at −78° C. After 30 min at the same temperature, the reaction was diluted with isopropyl alcohol/chloroform (4:1) co-solvent (30 mL) and saturated potassium sodium tartrate solution (10 mL) was added. The mixture was stirred at room temperature for 2 h and the organic layer was collected. The aqueous layer was extracted with isopropyl alcohol/chloroform (4:1) co-solvent (3×10 mL) and organic layer were combined, dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo and the residue was purified by column chromatography on a silica gel (MeOH:CH2Cl2=1:20 to1:10) to give adenosine analogue 15 (70.0 mg, 76%) as a white solid. mp: 215-218° C. (dec.) [α]25D +151.80° (c 0.23, CHCl3) UV (H2O) λmax 259.0 nm (ε 13998, pH 2), 260.0 nm (ε 15590, pH 7), 260.0 nm (ε 15579, pH 11); 1H NMR (400 MHz, CDCl3) δ 8.22 (s, 1H), 8.06 (d, J=2.4 Hz, 1H), 5.86 (dd, J=2.4 and 25.6 Hz, 1H), 5.42 (t, J=2.4 Hz, 1H), 4.93 (td, J=3.2 and 52.4 Hz, 1H), 4.92 (s, 1H, partially buried inside the H2O peak), 4.40 (td, J=3.2 and 10.8 Hz, 1H), 3.88-3.76 (m, 2H), 2.78 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 156.0, 152.5, 149.9, 146.1 (d, J=1.0 Hz), 141.1 (d, J=5.2 Hz), 117.9, 111.8, 95.9 (d, J=186.0 Hz), 72.9 (d, J=22.9 Hz), 61.8 (d, J=3.4 Hz), 57.6 (d, J 17.2 Hz), 51.1. Anal. Calcd. for C12H14FN5O2: C, 51.61; H, 5.05; N, 25.08. Found: C, 51.74; H, 5.09; N, 24.92.

Workup

  1. additionwas added
  2. customthe organic layer was collected
  3. extractionThe aqueous layer was extracted with isopropyl alcohol/chloroform (4:1) co-solvent (3×10 mL) and organic layer
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated in vacuo
  7. customthe residue was purified by column chromatography on a silica gel (MeOH:CH2Cl2=1:20 to1:10)

Sources & evidence

ORD record
ord-1b50fc73bb29491b8b3f24ac812d39ce
Source dataset
uspto-grants-2014_08
Patent number
US08816074B2

Reaction notes

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