Cesium carbonate → Tert-butyl 3-fluoro-4-iodophenylcarbamate

HRID 558998Notes

Reaction equation

HRID 558998 reaction equation
[I:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][C:3]=1[F:9].C([NH:14][C:15](=[O:17])[O-:16])(C)(C)C.[CH3:18][C:19]1(C)[C:45]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:20]1=2.C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1.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].CCOC(C)=O.O>[F:9][C:3]1[CH:4]=[C:5]([NH:14][C:15](=[O:17])[O:16][C:19]([CH3:45])([CH3:20])[CH3:18])[CH:6]=[CH:7][C:2]=1[I:1]

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 27370962,5-DiiodofluorobenzeneHCID 21252905Tert-butylcarbamate

Product 1

HCID 44203004Tert-butyl 3-fluoro-4-iodophenylcarbamateYield 531%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 2,5-diiodofluorobenzene (1.36 g, 3.90 mmol), tert-butylcarbamate (0.454 g, 3.88 mmol), xantphos (0.233 g, 0.40 mmol) and Cs2CO3 (dry powder, 2.48 g, 7.61 mmol) in THF (12 mL) was degassed with Ar before being charged with Pd2(dba)3 (0.071 g, 0.078 mmol). It was stirred at 75 C overnight. After being cooled to room temperature, water and EtOAc were added. The organic phase was separated, dried over Na2SO4, concentrated in vacuo. The residue was loaded to a flash column, eluted with 0-10% EtOAc in hexane to give tert-butyl 3-fluoro-4-iodophenylcarbamate (716 mg).

Workup

  1. customwas degassed with Ar
  2. customThe organic phase was separated
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. washeluted with 0-10% EtOAc in hexane

Sources & evidence

ORD record
ord-ad33550f1e94473ea2eb1afb0c841ed2
Source dataset
uspto-grants-2011_11
Patent number
US08063058B2

Reaction notes

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