Water → rac-tert-butyl 7,8-dihydroxy-2,3-diphenyl-7,8-dihydropyrido[2,3-b]pyrazine-5(6H)-carboxylate

HRID 2276609Notes

Reaction equation

HRID 2276609 reaction equation
[Mn]([O-])(=O)(=O)=O.[K+].[C:7]1([C:13]2[N:14]=[C:15]3[CH:28]=[CH:27][CH2:26][N:25]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[C:16]3=[N:17][C:18]=2[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.S(=O)(O)[O-:37].[Na+].[OH2:41]>[Cl-].C([N+](CCCC)(CCCC)C)CCC.C(Cl)Cl>[OH:41][CH:27]1[CH2:26][N:25]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[C:16]2=[N:17][C:18]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[C:13]([C:7]3[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=3)[N:14]=[C:15]2[CH:28]1[OH:37]

Participants

7

Reactant 4

HCID 962WaterHCID 516875Potassium PermanganateHCID 23665763Sodium BisulfiteHCID 66665728tert-Butyl 2,3-diphenylpyrido[2,3-b]pyrazine-5(6H)-carboxylate

Product 1

HCID 66665861rac-tert-butyl 7,8-dihydroxy-2,3-diphenyl-7,8-dihydropyrido[2,3-b]pyrazine-5(6H)-carboxylate

Reagents, catalysts & solvents 2

HCID 91822Tributylmethylammonium chlorideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of tributylmethylammonium chloride (728 mg, 3.09 mmol) in DCM (10 ml) was added potassium permanganate (488 mg, 3.09 mmol) portionwise over 10 minutes at room temperature. The reaction mixture was allowed to stir under an atmosphere of nitrogen for 30 minutes. The mixture was cooled down to 0° C. and treated dropwise with a solution of tert-butyl 2,3-diphenylpyrido[2,3-b]pyrazine-5(6H)-carboxylate (step 1)(700 mg, 1.816 mmol) in DCM (8 ml). The reaction was then left to stir for a further 2 hours at 0-5° C. under an atmosphere of nitrogen. A solution of sodium bisulfite (1134 mg, 10.90 mmol) in water (9 ml) was added dropwise at 0-5° C. to the reaction mixture. The mixture was filtered through Celite® (filter material) and washed with DCM (20 ml) and water (10 ml). The organic layer was separated and concentrated in vacuo to give a foamy solid. The crude material was purified by chromatography on silica eluting with 0-90% EtOAc/iso-hexane to afford the title compound;

Workup

  1. waitThe reaction was then left
  2. stirringto stir for a further 2 hours at 0-5° C. under an atmosphere of nitrogen
  3. filtrationThe mixture was filtered through Celite® (filter material)
  4. washwashed with DCM (20 ml) and water (10 ml)
  5. customThe organic layer was separated
  6. concentrationconcentrated in vacuo
  7. customto give a foamy solid
  8. customThe crude material was purified by chromatography on silica eluting with 0-90% EtOAc/iso-hexane

Sources & evidence

ORD record
ord-7fde1b8c807845df88817169c12a0aea
Source dataset
uspto-grants-2015_09
Patent number
US09132127B2

Reaction notes

Loading…