Cesium carbonate → HCID 68327931, compound

HRID 2403286Notes

Reaction equation

HRID 2403286 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[O:13][CH2:12][CH2:11][N:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:9]2)=[CH:4][C:3]=1[CH3:21].Br[C:23]1[CH:28]=[CH:27][C:26]([Br:29])=[CH:25][N:24]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1>[Br:29][C:26]1[CH:27]=[CH:28][C:23]([NH:1][C:2]2[CH:7]=[CH:6][C:5]([CH:8]3[O:13][CH2:12][CH2:11][N:10]([C:14]([O:16][C:17]([CH3:18])([CH3:20])[CH3:19])=[O:15])[CH2:9]3)=[CH:4][C:3]=2[CH3:21])=[N:24][CH:25]=1

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 693532,5-DibromopyridineHCID 68325506HCID 68325506, compound

Product 1

HCID 68327931HCID 68327931, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

tert-butyl (RS)-2-(4-amino-3-methylphenyl)morpholine-4-carboxylate (60 mg), 2,5-dibromopyridine (48.6 mg, CAS 624-28-2) and cesium carbonate (100 mg) were combined with dioxane (2 ml) to give a yellow suspension. The mixture was degassed by bubbling argon into the mixture for several minutes. Xantphos (7.12 mg) and tris(dibenzylideneacetone)dipalladium chloroform complex (6.37 mg) were then added. The reaction mixture was then capped and stirred at 80° C. for 1 hour. The crude reaction mixture was cooled to room temperature and filtered. The filtrate was concentrated in vacuo and the residue was purified by flash column chromatography (silica gel; gradient: 0% to 80% EtOAc in hexanes) to afford tert-butyl (RS)-2-(4-(5-bromopyridin-2-ylamino)-3-methylphenyl)morpholine-4-carboxylate (40 mg, 44%) as a colourless amorphous solid. MS (ISP): 450.2 ([{81Br}M+H]+), 448.1 ([{79Br}M+H]+), 394.3 ([{81Br}M+H—C4H8]+), 392.1 ([{79Br}M+H—C4H8]+).

Workup

  1. customto give a yellow suspension
  2. customThe mixture was degassed
  3. customby bubbling argon into the mixture for several minutes
  4. additionXantphos (7.12 mg) and tris(dibenzylideneacetone)dipalladium chloroform complex (6.37 mg) were then added
  5. customThe reaction mixture was then capped
  6. customThe crude reaction mixture
  7. temperaturewas cooled to room temperature
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated in vacuo
  10. customthe residue was purified by flash column chromatography (silica gel; gradient: 0% to 80% EtOAc in hexanes)

Sources & evidence

ORD record
ord-ed793cb1f9c947f8ba918412e13ab69c
Source dataset
uspto-grants-2014_08
Patent number
US08802673B2

Reaction notes

Loading…