4-[(1S)-2-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-1-(hydroxymethyl)ethyl]-6-(methyloxy)-1,4-dihydropyrido[2,3-b]pyrazin-3(2H)-one → 4-[(1S)-2-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-1-(hydroxymethyl)ethyl]-6-(methyloxy)pyrido[2,3-b]pyrazin-3(4H)-one

HRID 420690Notes

Reaction equation

HRID 420690 reaction equation
[CH3:1][C:2]([Si:5]([CH3:25])([CH3:24])[O:6][CH2:7][C@@H:8]([N:11]1[C:16](=[O:17])[CH2:15][NH:14][C:13]2[CH:18]=[CH:19][C:20]([O:22][CH3:23])=[N:21][C:12]1=2)[CH2:9][OH:10])([CH3:4])[CH3:3]>C(Cl)Cl.O=[Mn]=O>[CH3:4][C:2]([Si:5]([CH3:24])([CH3:25])[O:6][CH2:7][C@@H:8]([N:11]1[C:16](=[O:17])[CH:15]=[N:14][C:13]2[CH:18]=[CH:19][C:20]([O:22][CH3:23])=[N:21][C:12]1=2)[CH2:9][OH:10])([CH3:1])[CH3:3]

Participants

4

Reactant 1

HCID 582008614-[(1S)-2-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-1-(hydroxymethyl)ethyl]-6-(methyloxy)-1,4-dihydropyrido[2,3-b]pyrazin-3(2H)-one

Product 1

HCID 666584284-[(1S)-2-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-1-(hydroxymethyl)ethyl]-6-(methyloxy)pyrido[2,3-b]pyrazin-3(4H)-oneYield 92.2%

Reagents, catalysts & solvents 2

HCID 14801Manganese dioxideCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 4-[(1S)-2-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-1-(hydroxymethyl)ethyl]-6-(methyloxy)-1,4-dihydropyrido[2,3-b]pyrazin-3(2H)-one (494.1 g, 1.34 mol) and MnO2 (584.4 g, 6.72 mol) in DCM (18 L) was stirred at room temperature for 1 h. The mixture was filtered through celite and the filtrate was evaporated to give a purple/white solid. The crude was purified by column chromatography and mixtures of heptane and EtOAc as eluent to give of 451.6 g (66%) of 4-[(1S)-2-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-1-(hydroxymethyl)ethyl]-6-(methyloxy)pyrido[2,3-b]pyrazin-3(4H)-one.

Workup

  1. filtrationThe mixture was filtered through celite
  2. customthe filtrate was evaporated
  3. customto give a purple/white solid
  4. customThe crude was purified by column chromatography and mixtures of heptane and EtOAc as eluent

Sources & evidence

ORD record
ord-be39ae6504564f41946dfed58de723ed
Source dataset
uspto-grants-2012_01
Patent number
US08097628B2

Reaction notes

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