Cesium carbonate → HCID 86695816, compound

HRID 1051999Notes

Reaction equation

HRID 1051999 reaction equation
CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:41]1[O:50][C:44]2([CH2:49][CH2:48][NH:47][CH2:46][CH2:45]2)[O:43][CH2:42]1.[CH3:51][O:52][C:53](=[O:61])[C:54]1[CH:59]=[CH:58][C:57](Br)=[CH:56][CH:55]=1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CC(O)(C)C>[CH3:51][O:52][C:53](=[O:61])[C:54]1[CH:59]=[CH:58][C:57]([N:47]2[CH2:48][CH2:49][C:44]3([O:50][CH2:41][CH2:42][O:43]3)[CH2:45][CH2:46]2)=[CH:56][CH:55]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 12081Methyl 4-bromobenzoateHCID 674351,4-Dioxa-8-azaspiro(4.5)decaneHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl

Product 1

HCID 86695816HCID 86695816, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent2×HCID 6386tert-ButanolSolvent2×

Conditions

Temperature
120 °C

Procedure

Procedure adopted from Tetrahedron Lett., 2007, 48, 2519. A thick-walled glass reaction vessel was charged with palladium(II)acetate (157 mg, 0.698 mmol), X-Phos (332 mg, 0.698 mmol, 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl), cesium carbonate (4.55 g, 13.96 mmol) and 5:1 (v/v) toluene:t-BuOH (20 mL). The stirred contents were purged with nitrogen and a solution of 4-piperidone ethylene ketal (1.80 mL, 13.96 mmol) and methyl-4-bromobenzoate (3.30 g, 15.36 mmol) in 5:1 (v/v) toluene:t-BuOH (100 mL) was added. After stirring for 2 minutes, the vessel was sealed and the reaction mixture was heated at 120° C. for 18 hours. Upon cooling to room temperature, the reaction mixture was filtered through celite and the filtrate was concentrated. Elution through a flash column (silica gel 60, 230-400 mesh, 3:2 hexanes:EtOAc) gave the title compound as an off-white, crystalline solid (3.20 g, 83%).

Workup

  1. customA thick-walled glass reaction vessel
  2. customThe stirred contents were purged with nitrogen
  3. customthe vessel was sealed
  4. temperatureUpon cooling to room temperature
  5. filtrationthe reaction mixture was filtered through celite
  6. concentrationthe filtrate was concentrated
  7. washElution through a flash column (silica gel 60, 230-400 mesh, 3:2 hexanes:EtOAc)

Sources & evidence

ORD record
ord-93bb37fcec194be48a67de7615612d53
Source dataset
uspto-grants-2016_07
Patent number
US09388176B2

Reaction notes

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