Trimethylphosphine → 7-[(3aS,4R,6R,6aR)-6-(aminomethyl)-2,2-dimethylhexahydrocyclopenta[d][1,3]dioxol-4-yl]-7H-pyrrolo[2,3-d]pyrimidin-4-amine

HRID 1054526Notes

Reaction equation

HRID 1054526 reaction equation
[N:1]([CH2:4][C@@H:5]1[C@H:9]2[O:10][C:11]([CH3:14])([CH3:13])[O:12][C@H:8]2[C@H:7]([N:15]2[C:19]3[N:20]=[CH:21][N:22]=[C:23]([NH2:24])[C:18]=3[CH:17]=[CH:16]2)[CH2:6]1)=[N+]=[N-].P(C)(C)C>O1CCCC1>[NH2:1][CH2:4][C@@H:5]1[C@H:9]2[O:10][C:11]([CH3:14])([CH3:13])[O:12][C@H:8]2[C@H:7]([N:15]2[C:19]3[N:20]=[CH:21][N:22]=[C:23]([NH2:24])[C:18]=3[CH:17]=[CH:16]2)[CH2:6]1

Participants

4

Reactant 2

HCID 68983TrimethylphosphineHCID 867057457-[(3aS,4R,6R,6aR)-6-(azidomethyl)-2,2-dimethyl-hexahydrocyclopenta[d][1,3]dioxol-4-yl]-7H-pyrrolo[2,3-d]pyrimidin-4-amine

Product 1

HCID 678180027-[(3aS,4R,6R,6aR)-6-(aminomethyl)-2,2-dimethylhexahydrocyclopenta[d][1,3]dioxol-4-yl]-7H-pyrrolo[2,3-d]pyrimidin-4-amineYield 78%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 7-[(3aS,4R,6R,6aR)-6-(azidomethyl)-2,2-dimethyl-hexahydrocyclopenta[d][1,3]dioxol-4-yl]-7H-pyrrolo[2,3-d]pyrimidin-4-amine (527.5 mg, 1.6 mmol) in tetrahydrofuran (5 ml) under N2 was added 1M PMe3 in THF (3.2 ml, 3.2 mmol) and the reaction was stirred overnight. The reaction was quenched by the addition of H2O (1 ml), and stirred for 15 mins before being concentrated under reduced pressure. The crude material was purified by silica flash column chromatography, eluting with 2.5 to 20% 2M NH3 in MeOH in DCM to afford the title compound (376.9 mg, 78%) as a colorless gum: MS (ESI+) for C15H21N5O2 m/z 304.0 [M+H]+; LC purity 99% (ELS) (ret. time, solvent front); 1H NMR (500 MHz, MeOD) δ 7.26 (d, J=3.6 Hz, 1H), 8.07 (s, 1H), 6.61 (d, J=3.6 Hz, 1H), 4.97-5.06 (m, 1H), 4.90-4.97 (m, 1H), 4.55 (dd, J=7.3, 5.8 Hz, 1H), 2.82-2.91 (m, 1H), 2.70-2.81 (m, 1H), 2.39 (dt, J=12.6, 6.5 Hz, 1H), 2.26 (dt, J=12.6, 6.2 Hz, 1H), 1.93-2.10 (m, 1H), 1.54 (s, 3H), 1.25-1.35 (m, 3H).

Workup

  1. customThe reaction was quenched by the addition of H2O (1 ml)
  2. stirringstirred for 15 mins
  3. concentrationbefore being concentrated under reduced pressure
  4. customThe crude material was purified by silica flash column chromatography
  5. washeluting with 2.5 to 20% 2M NH3 in MeOH in DCM

Sources & evidence

ORD record
ord-7cc2e50cf11a4daeb3045c2e69743a05
Source dataset
uspto-grants-2016_07
Patent number
US09394310B2

Reaction notes

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