tert-Butyl carbazate → HCID 58382419, compound

HRID 1628064Notes

Reaction equation

HRID 1628064 reaction equation
CC(C1C=C(C(C)C)C(C2C(P(C(C)(C)C)C(C)(C)C)=CC=CC=2)=C(C(C)C)C=1)C.Br[C:32]1[N:33]=[C:34]2[CH:40]=[C:39]([C:41]3[CH:42]=[N:43][N:44]([CH3:46])[CH:45]=3)[N:38]([CH2:47][O:48][CH2:49][CH2:50][Si:51]([CH3:54])([CH3:53])[CH3:52])[C:35]2=[N:36][CH:37]=1.[NH:55]([C:57]([O:59][C:60]([CH3:63])([CH3:62])[CH3:61])=[O:58])[NH2:56].CC([O-])(C)C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[CH3:46][N:44]1[CH:45]=[C:41]([C:39]2[N:38]([CH2:47][O:48][CH2:49][CH2:50][Si:51]([CH3:54])([CH3:53])[CH3:52])[C:35]3=[N:36][CH:37]=[C:32]([NH:56][NH:55][C:57]([O:59][C:60]([CH3:63])([CH3:62])[CH3:61])=[O:58])[N:33]=[C:34]3[CH:40]=2)[CH:42]=[N:43]1

Participants

7

Reactant 4

HCID 70091tert-Butyl carbazateHCID 11618717Di-tert-butyl(2',4',6'-tris(propan-2-yl)-(1,1'-biphenyl)-2-yl)phosphaneHCID 23676156Sodium t-butoxideHCID 58382157HCID 58382157, compound

Product 1

HCID 58382419HCID 58382419, compoundYield 33%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a flask was added Pd2 dba3 (0.309 g, 0.338 mmol), tert-Butyl X-Phos (0.287 g, 0.676 mmol) and 1,4-dioxane (25 mL). The mixture was heated to about 80° C. for about 10 min and then 2-bromo-6-(1-methyl-1H-pyrazol-4-yl)-5-((2-(trimethylsilyl)ethoxy)methyl)-5H-pyrrolo[2,3-b]pyrazine (1.38 g, 3.38 mmol, prepared using B from Preparation #A.1 and C), tert-butyl hydrazinecarboxylate (0.670 g, 5.07 mmol) and NaOt-Bu (0.487 g, 5.07 mmol) were then added and mixture was heated at about 80° C. for about 1 h. The mixture was cooled, filtered through Celite® and the filter pad was rinsed with EtOAc. The filtrate was concentrated in vacuo then purified by flash chromatography (40 g silica column eluting with 0 to 100% EtOAc/DCM to provide tert-butyl 2-(6-(1-methyl-1H-pyrazol-4-yl)-5-((2-(trimethylsilyl)ethoxy)methyl)-5H-pyrrolo[2,3-b]pyrazin-2-yl)hydrazinecarboxylate (0.510 g, 33%): LC/MS (Table 2, Method c) Rt=1.59 min; MS m/z 460 (M+H)+.

Workup

  1. temperaturemixture was heated at about 80° C. for about 1 h
  2. temperatureThe mixture was cooled
  3. filtrationfiltered through Celite®
  4. washthe filter pad was rinsed with EtOAc
  5. concentrationThe filtrate was concentrated in vacuo
  6. customthen purified by flash chromatography (40 g silica column
  7. washeluting with 0 to 100% EtOAc/DCM

Sources & evidence

ORD record
ord-da5cf6e603ae4288b73da764b32d9c30
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Reaction notes

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