Triisopropyl borate → 1,3-Dimethyl-2,4-dioxo-6-(2-(tritylthio)ethyl)-2,3,4,6-tetrahydro-1H-pyrrolo[3,4-d]pyrimidin-5-ylboronic acid

HRID 2201287Notes

Reaction equation

HRID 2201287 reaction equation
[CH3:1][N:2]1[C:7]2=[CH:8][N:9]([CH2:11][CH2:12][S:13][C:14]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)[C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:10]=[C:6]2[C:5](=[O:33])[N:4]([CH3:34])[C:3]1=[O:35].[Li+].CC([N-]C(C)C)C.[B:44](OC(C)C)([O:49]C(C)C)[O:45]C(C)C>C1COCC1>[CH3:1][N:2]1[C:7]2=[CH:8][N:9]([CH2:11][CH2:12][S:13][C:14]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)([C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=3)[C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C:10]([B:44]([OH:49])[OH:45])=[C:6]2[C:5](=[O:33])[N:4]([CH3:34])[C:3]1=[O:35]

Participants

5

Reactant 3

HCID 21531Triisopropyl borateHCID 2724682Lithium diisopropylamideHCID 867235211,3-Dimethyl-6-(2-(tritylthio)ethyl)-1H-pyrrolo[3,4-d]pyrimidine-2,4(3H,6H)-dione

Product 1

HCID 867235221,3-Dimethyl-2,4-dioxo-6-(2-(tritylthio)ethyl)-2,3,4,6-tetrahydro-1H-pyrrolo[3,4-d]pyrimidin-5-ylboronic acid

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

1,3-Dimethyl-6-(2-(tritylthio)ethyl)-1H-pyrrolo[3,4-d]pyrimidine-2,4(3H,6H)-dione (step 2)(3.6 g, 7.47 mmol) was dissolved in anhydrous THF (67.3 mL) at room temperature in an oven dried flask. The flask was evacuated and backfilled with nitrogen (×3) and cooled to −78° C. LDA (0.719 M, 16.63 mL, 11.96 mmol) was added over 10 mins followed by triisopropyl borate (2.76 mL, 11.96 mmol) and the reaction aged for 2 hr at −78° C. The reaction was quenched with saturated NH4Cl solution (60 mL) added via syringe under nitrogen and the mixture was warmed to room temperature and stirred overnight under nitrogen. The mixture was then diluted DCM (400 mL). The layers were separated and the aqueous extracted with DCM (2×100 mL). The combined organics were passed through a hydrophobic frit and the solvent was reduced to ˜20 mL under reduced pressure and EtOAc (100 mL) added to the resulting red oil. Reduction of solvent volume under reduced pressure to ˜25 mL afforded precipitation of a white solid. The solid was collected by reduced pressure filtration, washed with EtOAc (10 mL) and dried under vacuum 50° C. for 16 h to afford the title compound;

Workup

  1. customdried flask
  2. customThe flask was evacuated
  3. customThe reaction was quenched with saturated NH4Cl solution (60 mL)
  4. additionadded via syringe under nitrogen
  5. temperaturethe mixture was warmed to room temperature
  6. customThe layers were separated
  7. extractionthe aqueous extracted with DCM (2×100 mL)
  8. additionadded to the resulting red oil
  9. customReduction of solvent volume under reduced pressure to ˜25 mL afforded
  10. customprecipitation of a white solid
  11. filtrationThe solid was collected by reduced pressure filtration
  12. washwashed with EtOAc (10 mL)
  13. customdried under vacuum 50° C. for 16 h

Sources & evidence

ORD record
ord-0024c3cb8e0847bf9c2b58e3db6fccef
Source dataset
uspto-grants-2016_06
Patent number
US09359381B2

Reaction notes

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