Cesium carbonate → Tert-butyl 2-morpholin-4-yl-[1,2,4]triazolo[1,5-a]pyridin-6-ylcarbamate

HRID 588432Notes

Reaction equation

HRID 588432 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([N:8]=[C:9]([N:11]3[CH2:16][CH2:15][O:14][CH2:13][CH2:12]3)[N:10]=2)[CH:7]=1.[C:17](=[O:24])([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[NH2:18].C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:20]([O:19][C:17](=[O:24])[NH:18][C:2]1[CH:3]=[CH:4][C:5]2[N:6]([N:8]=[C:9]([N:11]3[CH2:16][CH2:15][O:14][CH2:13][CH2:12]3)[N:10]=2)[CH:7]=1)([CH3:23])([CH3:22])[CH3:21]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 717438774-(6-Bromo-[1,2,4]triazolo[1,5-A]pyridin-2-YL)morpholine

Product 1

HCID 89464434Tert-butyl 2-morpholin-4-yl-[1,2,4]triazolo[1,5-a]pyridin-6-ylcarbamateYield 20.4%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

A mixture of 4-(6-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-yl)morpholine (200 mg, 706 μmol), tert-butyl carbamate (99.3 mg, 848 μmol) and cesium carbonate (322 mg, 989 μmol) was purged several times with argon, then tris(dibenzylideneacetone)dipalladium(0) (12.9 mg, 14.1 μmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (16.3 mg, 28.3 μmol) were added and the mixture was purged with argon again, the vessel was then capped. The resulting mixture was refluxed for 20 hours. The mixture was evaporated to dryness under reduced pressure. Final purification by flash chromatography (20 g silicagel column using heptane/ethyl acetate 70-100% as eluent) afforded (2-morpholin-4-yl-[1,2,4]triazolo[1,5-a]pyridin-6-yl)-carbamic acid tert-butyl ester (46 mg, 20.4%) as yellow solid. Mp.: 166° C. MS: m/z=320.0 (M+H+).

Workup

  1. customwas purged several times with argon
  2. customthe mixture was purged with argon again
  3. customthe vessel was then capped
  4. temperatureThe resulting mixture was refluxed for 20 hours
  5. customThe mixture was evaporated to dryness under reduced pressure
  6. customFinal purification by flash chromatography (20 g silicagel column using heptane/ethyl acetate 70-100% as eluent)

Sources & evidence

ORD record
ord-0f2fa10d51374d6f8b55520edc87ec91
Source dataset
uspto-grants-2016_01
Patent number
US09227970B2

Reaction notes

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