Cesium carbonate → HCID 118390791, compound

HRID 590867Notes

Reaction equation

HRID 590867 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].[C:7]([O:11][C:12](=[O:45])[N:13]([C:16]1[C:20]2[CH:21]=[N:22][C:23](Cl)=[CH:24][C:19]=2[N:18]([C:26]([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[N:17]=1)[CH2:14][CH3:15])([CH3:10])([CH3:9])[CH3:8].[C:46](=[O:56])([O:48][CH2:49][C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1)[NH2:47].C1(P(C2CCCCC2)C2C(OC)=CC=C(OC)C=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1>O1CCOCC1>[C:7]([O:11][C:12](=[O:45])[N:13]([C:16]1[C:20]2[CH:21]=[N:22][C:23]([NH:47][C:46]([O:48][CH2:49][C:50]3[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=3)=[O:56])=[CH:24][C:19]=2[N:18]([C:26]([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[N:17]=1)[CH2:14][CH3:15])([CH3:10])([CH3:9])[CH3:8]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 12136Benzyl carbamateHCID 25112535BrettphosHCID 118390789HCID 118390789, compound

Product 1

HCID 118390791HCID 118390791, compoundYield 37.1%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A 20 mL microwave vial was charged with cesium carbonate (907 mg, 2.78 mmol), tert-butyl(6-chloro-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-yl)(ethyl)carbamate (500 mg, 0.928 mmol), benzyl carbamate (421 mg, 2.78 mmol), 2-(dicyclohexylphosphino)3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl (34.9 mg, 0.065 mmol) and BrettPhos-G3-Pd (58.9 mg, 0.065 mmol). Dioxane (10 ml) was added, the vial was flushed with argon, capped and the contents heated to 100° C. with stirring for 16 h. The reaction mixture was diluted with DCM/i-PrOH (4:1, 50 mL) and washed with brine (2×50 mL), dried (MgSO4), filtered and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel (ISCO; 24 g prepacked) eluting with ethyl acetate/hexanes to afford tert-butyl(6-(((benzyloxy)carbonyl)amino)-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-yl)(ethyl)carbamate (225 mg, 0.344 mmol, 37.1% yield) as a white solid. MS ESI calc'd. For C40H40N5O4 [M+H]+ 654. found 654.

Workup

  1. customthe vial was flushed with argon
  2. customcapped
  3. additionThe reaction mixture was diluted with DCM/i-PrOH (4:1, 50 mL)
  4. washwashed with brine (2×50 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customthe solvent was evaporated under reduced pressure
  8. customThe resulting residue was purified by flash column chromatography on silica gel (ISCO; 24 g prepacked)
  9. washeluting with ethyl acetate/hexanes

Sources & evidence

ORD record
ord-cd6d87278089452183a986a06b5daa22
Source dataset
uspto-grants-2016_01
Patent number
US09233979B2

Reaction notes

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