Triphenylphosphine → HCID 86612256, compound

HRID 1623127Notes

Reaction equation

HRID 1623127 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH2:20][C:21]1[C:26]2[N:27]=[C:28]([CH2:35][CH2:36][CH3:37])[N:29]([CH2:30][CH2:31][CH2:32][CH2:33]O)[C:25]=2[C:24]([CH3:38])=[C:23]([CH3:39])[N:22]=1.[C:40]([O:44][C:45]([O:47][NH:48][C:49](=[O:55])[O:50][C:51]([CH3:54])([CH3:53])[CH3:52])=[O:46])([CH3:43])([CH3:42])[CH3:41].N(C(OC(C)C)=O)=NC(OC(C)C)=O>CN(C=O)C>[NH2:20][C:21]1[C:26]2[N:27]=[C:28]([CH2:35][CH2:36][CH3:37])[N:29]([CH2:30][CH2:31][CH2:32][CH2:33][N:48]([O:47][C:45]([O:44][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:46])[C:49](=[O:55])[O:50][C:51]([CH3:54])([CH3:53])[CH3:52])[C:25]=2[C:24]([CH3:38])=[C:23]([CH3:39])[N:22]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylate2×HCID 2728863tert-Butyl (((1,1-dimethylethoxy)carbonyl)oxy)carbamateHCID 69507048HCID 69507048, compound

Product 1

HCID 86612256HCID 86612256, compoundYield 82.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

Triphenylphosphine (0.845 g, 3.22 mmol, 1.1 eq), 4-(4-amino-6,7-dimethyl-2-propyl-1H-imidazo[4,5-c]pyridin-1-yl)butan-1-ol (0.81 g, 2.93 mmol), and tert-butyl N-(tert-butoxycarbonyloxy)carbamate (0.751 g, 3.22 mmol) were dissolved in DMF and cooled to 0° C. Diisopropyl azodicarboxylate (0.634 mL, 3.22 mmol) was added dropwise over 10 minutes to the reaction mixture and was allowed to warm to ambient temperature and stirred overnight. Analysis by HPLC indicated the reaction was incomplete. An additional amount of reagents (0.5 eq) were added to the reaction mixture (cooled to 0° C. before addition of the diisopropyl azodicarboxylate) and stirred for an additional 2 hours. The reaction mixture was concentrated under reduced pressure, dissolved in ethyl acetate (150 mL), washed with a water and brine mixture (1:1, 4×30 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on a BIOTAGE HORIZON High-Performance Flash Chromatography instrument (silica gel, eluting with 2-30% CMA in chloroform) and concentrated under reduced pressure to provide 1.19 g of tert-butyl 4-(4-amino-6,7-dimethyl-2-propyl-1H-imidazo[4,5-c]pyridin-1-yl)butyl[(tert-butoxycarbonyl)oxy]carbamate.

Workup

  1. temperatureto warm to ambient temperature
  2. stirringstirred for an additional 2 hours
  3. concentrationThe reaction mixture was concentrated under reduced pressure
  4. dissolutiondissolved in ethyl acetate (150 mL)
  5. washwashed with a water and brine mixture (1:1, 4×30 mL)
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by column chromatography on a BIOTAGE HORIZON High-Performance Flash Chromatography instrument (silica gel, eluting with 2-30% CMA in chloroform)
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-8948a244bddf4d049469450203961cc5
Source dataset
uspto-grants-2014_07
Patent number
US08778963B2

Reaction notes

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