Cesium carbonate → HCID 178496594, compound

HRID 2074197Notes

Reaction equation

HRID 2074197 reaction equation
[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([NH:6][C:7](=[O:19])[N:8]2[C@H:11]2[CH2:16][CH2:15][C@H:14]([O:17][CH3:18])[CH2:13][CH2:12]2)=[C:4]([Cl:20])[N:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.Br[C:74]1[CH:75]=[C:76]([CH:79]=[CH:80][C:81]=1[N+:82]([O-:84])=[O:83])[C:77]#[N:78]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:20][C:4]1[N:3]=[C:2]([NH:1][C:80]2[CH:79]=[C:76]([CH:75]=[CH:74][C:81]=2[N+:82]([O-:84])=[O:83])[C:77]#[N:78])[N:10]=[C:9]2[C:5]=1[NH:6][C:7](=[O:19])[N:8]2[C@H:11]1[CH2:12][CH2:13][C@H:14]([O:17][CH3:18])[CH2:15][CH2:16]1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 184132163-Bromo-4-nitrobenzonitrileHCID 178496595HCID 178496595, compound

Product 1

HCID 178496594HCID 178496594, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To an oven-dried 250 mL round bottom flask was added 2-amino-6-chloro-9-(trans-4-methoxycyclohexyl)-7H-purin-8(9H)-one (crude, 3.65 g, 12.28 mmol, 1 equiv.) in anhydrous toluene (50 mL), then freshly grounded cesium carbonate (6 g, 18.43 mmol, 1.5 equiv.) with stirring at room temperature under Ar. Pd(OAc)2 (1.24 g, 1.84 mmol, 0.15 equiv.), racemic BINAP (2.67 g, 4.3 mmol, 0.35 equiv.) and 3-bromo-4-nitro-benzonitrile (3.6 g, 15.96 mmol, 1.3 eq) were all added as solids. The reaction was performed under a flow of Argon, with heating at 100° C. for two days. The reaction mixture was cooled to room temperature, then concentrated in vacuo and the resulting residue was purified using flash chromatography (silica gel, gradient elution 10% EtOAc in hexanes to 50% EtOAc in hexanes) to give the desired product as an orange solid (50% yield). MS (EI) m/z 444 (MH)+.

Workup

  1. additionall added as solids
  2. temperatureThe reaction mixture was cooled to room temperature
  3. concentrationconcentrated in vacuo
  4. customthe resulting residue was purified
  5. washflash chromatography (silica gel, gradient elution 10% EtOAc in hexanes to 50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-3cd9ac41beed4d779c7d2ba0a2539c46
Source dataset
uspto-grants-2011_04
Patent number
US07919490B2

Reaction notes

Loading…