Cesium carbonate → HCID 69357547, compound

HRID 852526Notes

Reaction equation

HRID 852526 reaction equation
[C:1]([O:5][C:6](=[O:15])[C:7]1[CH:12]=[C:11](I)[CH:10]=[C:9]([Br:14])[CH:8]=1)([CH3:4])([CH3:3])[CH3:2].C([O-])([O-])=O.[Cs+].[Cs+].[C:22]1(=[O:28])[NH:27][CH2:26][CH2:25][CH2:24][CH2:23]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].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>[C:1]([O:5][C:6](=[O:15])[C:7]1[CH:12]=[C:11]([N:27]2[CH2:26][CH2:25][CH2:24][CH2:23][C:22]2=[O:28])[CH:10]=[C:9]([Br:14])[CH:8]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 126652-PiperidoneHCID 574859731,1-Dimethylethyl 3-bromo-5-iodobenzoate

Product 1

HCID 69357547HCID 69357547, compoundYield 68%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
60 °C

Procedure

A flask was charged under nitrogen with 3-bromo-5-iodo-benzoic acid tert-butyl ester (D8b) (6.42 g, 16.7 mmol, 1 equiv), Cs2CO3 (7.6 g, 23.4 mmol, 1.4 equiv), tris(dibenzylideneacetone)dipalladium(0) (307 mg, 0.33 mmol, 0.02 equiv), Xantphos (578 mg, 1 mmol, 0.06 equiv) and dioxan (120 ml). δ-Valerolactam (1.9 ml, 20 mmol, 1.2 equiv) was then added via syringe and the resulting mixture was stirred at 60° C. for 40 h then cooled to room temperature and concentrated in vacuo. The residue was partitioned between H2O and AcOEt and the aqueous phase was re-extracted with AcOEt. The combined organic solutions were dried over MgSO4 and concentrated in vacuo Purification by flash chromatography on silica gel (iso-hexane/AcOEt: 3/1 to 1/1) gave 3-bromo-5-(2-oxo-piperidin-1-yl)-benzoic acid tert-butyl ester (D10) (4 g, 68%) as a white solid. RT=2.88 min

Workup

  1. temperaturethen cooled to room temperature
  2. concentrationconcentrated in vacuo
  3. customThe residue was partitioned between H2O and AcOEt
  4. extractionthe aqueous phase was re-extracted with AcOEt
  5. dry with materialThe combined organic solutions were dried over MgSO4
  6. concentrationconcentrated in vacuo Purification by flash chromatography on silica gel (iso-hexane/AcOEt: 3/1 to 1/1)

Sources & evidence

ORD record
ord-992bc69450414799b60da6be50d6ae1a
Source dataset
uspto-grants-2007_08
Patent number
US07253198B2

Reaction notes

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