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

HRID 1802004
Notes
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Reaction equation

HRID 1802004 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]
ParticipantsProcedureWorkupSources & evidenceReaction notes

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)palladiumCatalyst
HCID 962WaterSolvent
HCID 8028TetrahydrofuranSolvent
HCID 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-a1c681c84abd430588ffe495c70d98dd
Source dataset
uspto-grants-2013_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08349860B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes