Selectfluor → Iminodicarbonsaure

HRID 596019Notes

Reaction equation

HRID 596019 reaction equation
[C:1]([NH:4][C:5]([OH:7])=[O:6])([OH:3])=[O:2].[C:8]([O:12][C:13]([NH:15][C:16]1[C:17]([C:36]2[CH:44]=[CH:43][C:39]([C:40]([O-:42])=[O:41])=[C:38]([F:45])[CH:37]=2)=[N:18][C:19]([CH:22]2[CH2:27][CH2:26][C:25]([O:28][Si](CC)(CC)CC)=[CH:24][CH2:23]2)=[CH:20][N:21]=1)=[O:14])([CH3:11])([CH3:10])[CH3:9].[B-](F)(F)(F)[F:47].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1>C(#N)C>[C:1]([NH:4][C:5]([OH:7])=[O:6])([OH:3])=[O:2].[C:8]([O:12][C:13]([NH:15][C:16]1[C:17]([C:36]2[CH:44]=[CH:43][C:39]([C:40]([O-:42])=[O:41])=[C:38]([F:45])[CH:37]=2)=[N:18][C:19]([CH:22]2[CH2:23][CH2:24][C:25](=[O:28])[CH:26]([F:47])[CH2:27]2)=[CH:20][N:21]=1)=[O:14])([CH3:9])([CH3:11])[CH3:10]

Participants

6

Reactant 3

HCID 2724933SelectfluorHCID 13267551IminodicarbonsaureHCID 1317346154-(3-((Tert-butoxycarbonyl)amino)-6-(4-((triethylsilyl)oxy)cyclohex-3-en-1-yl)pyrazin-2-yl)-2-fluorobenzoate

Product 2

HCID 13267551IminodicarbonsaureHCID 1317346174-(3-((Tert-butoxycarbonyl)amino)-6-(3-fluoro-4-oxocyclohexyl)pyrazin-2-yl)-2-fluorobenzoate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of imidodicarbonic acid, 4-(3-((tert-butoxycarbonyl)amino)-6-(4-((triethylsilyl)oxy)cyclohex-3-en-1-yl)pyrazin-2-yl)-2-fluorobenzoate, 1,3-bis(1,1-dimethylethyl) ester (12.1 g, 17.29 mmol) in acetonitrile (57.6 mL) was added Selectfluor® (7.96 g, 22.47 mmol) at 0° C. The reaction mixture was warmed up to room temperature and stirred overnight. After quenched with sat. NaHCO3 solution, the reaction mixture was extracted with EtOAc. The organic layer was washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo to provide imidodicarbonic acid, 4-(3-((tert-butoxycarbonyl)amino)-6-(3-fluoro-4-oxocyclohexyl)pyrazin-2-yl)-2-fluorobenzoate, 1,3-bis(1,1-dimethylethyl) ester (10.44 g, 17.29, 100%), which was used for the next step without further purification. LCMS (m/z, neutral-nonpolar method): 604.3 (MH+), 1.12 min.

Workup

  1. customAfter quenched with sat. NaHCO3 solution
  2. extractionthe reaction mixture was extracted with EtOAc
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-4c0902b38c534d319d95e2d71bfafc1d
Source dataset
uspto-grants-2016_01
Patent number
US09242996B2

Reaction notes

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