Cesium carbonate → [2-(3-Methoxy-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-7-yl]-carbamic acid tert-butyl ester

HRID 1802261Notes

Reaction equation

HRID 1802261 reaction equation
Br[C:2]1[CH:7]=[CH:6][N:5]2[N:8]=[C:9]([C:11]3[CH:16]=[CH:15][CH:14]=[C:13]([O:17][CH3:18])[CH:12]=3)[N:10]=[C:4]2[CH:3]=1.[C:19](=[O:26])([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])[NH2:20].C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>O1CCOCC1.CCOC(C)=O.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:22]([O:21][C:19](=[O:26])[NH:20][C:2]1[CH:7]=[CH:6][N:5]2[N:8]=[C:9]([C:11]3[CH:16]=[CH:15][CH:14]=[C:13]([O:17][CH3:18])[CH:12]=3)[N:10]=[C:4]2[CH:3]=1)([CH3:25])([CH3:24])[CH3:23]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 677747487-Bromo-2-(3-methoxyphenyl)-[1,2,4]triazolo[1,5-a]pyridine

Product 1

HCID 67776674[2-(3-Methoxy-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-7-yl]-carbamic acid tert-butyl esterYield 51%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A solution of 7-bromo-2-(3-methoxy-phenyl)-[1,2,4]triazolo[1,5-a]pyridine (5.0 g, 16.4 mmol), tert-butyl carbamate (2.88 g, 24.7 mmol) and cesium carbonate (10.6 g, 32.9 mmol) in dioxane (85 ml) was degassed well with argon for 20 min at 25° C. To this solution was then added tris(dibenzylideneacetone)dipalladium(0) (3.0 g, 3.28 mmol) and xantphos (3.8 g, 6.57 mmol), and the resulting mixture was degassed again with argon for another 20 min. The reaction mixture was heated at 100° C. under argon atmosphere for 16 h. The reaction mixture was diluted with EtOAc (500 ml). The organic layer was washed successively with water (2×250 ml) and brine (100 ml), dried over anhydrous Na2SO4, filtered, and evaporated in vacuum. The crude material thus obtained was purified by column chromatography over silica gel (20-40% EtOAc/hexane) to afford [2-(3-methoxy-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-7-yl]-carbamic acid tert-butyl ester (2.8 g, 51%) as yellow solid. LC-MS: m/z=341 [M+H]+.

Workup

  1. washThe organic layer was washed successively with water (2×250 ml) and brine (100 ml)
  2. dry with materialdried over anhydrous Na2SO4
  3. filtrationfiltered
  4. customevaporated in vacuum
  5. customThe crude material thus obtained
  6. customwas purified by column chromatography over silica gel (20-40% EtOAc/hexane)

Sources & evidence

ORD record
ord-142d63a55898406795e269b71096a4bd
Source dataset
uspto-grants-2013_01
Patent number
US08349824B2

Reaction notes

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