Acetonitrile → HCID 118453815, compound

HRID 1487262Notes

Reaction equation

HRID 1487262 reaction equation
[NH2:1][C:2]1[C:3]2[N:14]([CH2:15][O:16][CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH:13]=[C:12]([CH2:24][CH2:25][CH2:26][CH2:27][OH:28])[C:4]=2[N:5]=[C:6]([CH2:8][CH2:9][CH2:10][CH3:11])[N:7]=1.C[N+]1([O-])CCOCC1.C(#N)C>C(Cl)Cl.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[NH2:1][C:2]1[C:3]2[N:14]([CH2:15][O:16][CH2:17][C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)[CH:13]=[C:12]([CH2:24][CH2:25][CH2:26][CH:27]=[O:28])[C:4]=2[N:5]=[C:6]([CH2:8][CH2:9][CH2:10][CH3:11])[N:7]=1

Participants

6

Reactant 3

HCID 6342AcetonitrileHCID 82029Methyl morpholine oxide3×HCID 118453790HCID 118453790, compound

Product 1

HCID 118453815HCID 118453815, compoundYield 30.5%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalyst3×HCID 6344DichloromethaneSolvent4×

Procedure

A mixture of 4-(4-amino-5-((benzyloxy)methyl)-2-butyl-5H-pyrrolo[3,2-d]pyrimidin-7-yl)butan-1-ol (884 mg, 2.311 mmol), N-methylmorpholine N-Oxide (420 mg, 3.59 mmol), powdered 4 Å molecular sieves and tetrapropylammonium perruthenate (58 mg, 0.165 mmol) was placed under nitrogen and a mixture of anhydrous dichloromethane (27 mL) and anhydrous acetonitrile (3 mL) added. The reaction mixture was stirred at ambient temperature for 2 hours, Additional N-methylmorpholine N-Oxide (390 mg, 3.33 mmol) and tetrapropylammonium perruthenate (38 mg, 0.108 mmol) in anhydrous DCM (5 mL) was added and the reaction mixture stirred at ambient temperature for a further 2 hours. Additional N-methylmorpholine N-Oxide (130 mg, 1.11 mmol) and tetrapropylammonium perruthenate (100 mg, 0.284 mmol) were added and the reaction mixture stirred at ambient temperature for a further 30 mins, The reaction mixture was filtered through Celite and the cake washed with DCM three times. The reaction solvent was removed in vacuo and the residue dissolved in DCM and passed through Celite a second time. The cake was washed with DCM three times and the solvent removed in vacuo to give a black gum. The sample was dissolved in dichloromethane and purified by chromatography on on silica (100 g) using a gradient of 0-25% methanol-dichloromethane over 40 mins. The appropriate fractions were combined and evaporated in vacuo to give an orange gum with a black tinge. The sample was dissolved in dichloromethane and purified by chromatography on on silica (100 g) using a gradient of 0-25% methanol-dichloromethane over 80 mins. The appropriate fractions were combined and evaporated in vacuo to give the title compound as a pale yellow gum (268 mg).

Workup

  1. additionadded
  2. stirringthe reaction mixture stirred at ambient temperature for a further 2 hours
  3. stirringthe reaction mixture stirred at ambient temperature for a further 30 mins
  4. filtrationThe reaction mixture was filtered through Celite
  5. washthe cake washed with DCM three times
  6. customThe reaction solvent was removed in vacuo
  7. dissolutionthe residue dissolved in DCM
  8. washThe cake was washed with DCM three times
  9. customthe solvent removed in vacuo
  10. customto give a black gum
  11. custompurified by chromatography on on silica (100 g)
  12. customover 40 mins
  13. customevaporated in vacuo
  14. customto give an orange gum with a black tinge
  15. custompurified by chromatography on on silica (100 g)
  16. customover 80 mins
  17. customevaporated in vacuo

Sources & evidence

ORD record
ord-0124b5e99c9e4beab382344d47bfb4c8
Source dataset
uspto-grants-2016_08
Patent number
US09428512B2

Reaction notes

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