Cesium carbonate → HCID 69359925, compound

HRID 852593

Reaction equation

HRID 852593 reaction equation
COC(=O)[C:4]1[CH:9]=[C:8](I)[CH:7]=[C:6]([Br:11])[CH:5]=1.[C:13]([O-:16])([O-])=[O:14].[Cs+].[Cs+].[CH3:19][C:20]1(C)[C:46]2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=C[C:21]1=2.[C:61]1([CH:67]2[CH2:72][NH:71][C:70](=[O:73])[CH2:69][CH2:68]2)[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=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].C1(C)C=CC=CC=1>[Br:11][C:6]1[CH:7]=[C:8]([CH:9]=[C:4]([N:71]2[CH2:72][CH:67]([C:61]3[CH:62]=[CH:63][CH:64]=[CH:65][CH:66]=3)[CH2:68][CH2:69][C:70]2=[O:73])[CH:5]=1)[C:13]([O:16][C:20]([CH3:46])([CH3:21])[CH3:19])=[O:14]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 32796944-Phenyl-delta-valerolactamHCID 21942573Methyl 3-bromo-5-iodobenzoate

Product 1

HCID 69359925HCID 69359925, compoundYield 557.7%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A flask was charged under nitrogen with 3-bromo-5-iodo-benzoic acid methyl ester (D8b) (840 mg, 2.2 mmol, 1.1 equiv), Cs2CO3 (900 mg, 2.8 mmol, 1.4 equiv), tris(dibenzylideneacetone)dipalladium(0) (92 mg, 0.1 mmol, 0.05 equiv), Xantphos (120 mg, 0.2 mmol, 0.1 equiv) and toluene (40 ml). 5-Phenyl-2-piperidinone (Koelsch, J. Am. Chem. Soc. 1943, (65), 2093, 350 mg, 2 mmol, 1 equiv) was then added and the resulting mixture was stirred at 100° C. for 2.5 h then cooled to room temperature and concentrated in vacuo. The residue was partitioned between AcOEt and a saturated aqueous NaHCO3 solution. The layers were separated and the organic phase was dried over MgSO4 and concentrated in vacuo to give a solid residue. Purification of the residue by flash chromatography on silica gel (iso-hexane/AcOEt: 4/1 to 1/1) gave 1,1-dimethylethyl 3-bromo-5-(2-oxo-5-phenyl-1-piperidinyl)benzoate (D191) (480 mg, 51%) as a white solid. [M+H]+=432.2, RT=3.82 min.

Workup

  1. temperaturethen cooled to room temperature
  2. concentrationconcentrated in vacuo
  3. customThe residue was partitioned between AcOEt
  4. customThe layers were separated
  5. dry with materialthe organic phase was dried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customto give a solid residue
  8. customPurification of the residue by flash chromatography on silica gel (iso-hexane/AcOEt: 4/1 to 1/1)

Sources & evidence

ORD record
ord-76575696e7d948069c89719055d3767c
Source dataset
uspto-grants-2007_08
Patent number
US07253198B2

Linked notes

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