Binol → HCID 58181232, compound

HRID 1465441Notes

Reaction equation

HRID 1465441 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([I:8])=[CH:4][CH:3]=1.[CH:9]12[CH2:15][CH:12]([NH:13][CH2:14]1)[CH2:11][N:10]2[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17].C1C=C2C=CC(O)=C(C3C4C(=CC=CC=4)C=CC=3O)C2=CC=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>[Cu]I.CN(C)C=O>[I:8][C:5]1[CH:6]=[CH:7][C:2]([N:13]2[CH2:14][CH:9]3[CH2:15][CH:12]2[CH2:11][N:10]3[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 11762BinolHCID 12208p-Diiodobenzene2×HCID 62657Potassium Phosphate, TribasicHCID 2760898(1S,4S)-tert-butyl 2,5-diazabicyclo(2.2.1)heptane-2-carboxylate

Product 1

HCID 58181232HCID 58181232, compoundYield 33.1%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1,4-diiodobenzene (9.98 g, 30.3 mmol), tert-butyl 2,5-diazabicyclo[2.2.1]heptane-2-carboxylate (2.0 g, 10.1 mmol), copper (I) iodide (434 mg, 3.03 mmol), 1,1′-bi-2-naphthol (867 mg, 3.03 mg), tripotassium phosphate (5.14 g, 24.2 mmol) and anhydrous N,N-dimethylformamide (50 ml) was stirred at 80° C. for 2 days. 1,4-Diiodobenzene (3.33 g, 10.1 mmol) was added, and the mixture was stirred at 90° C. overnight. After cooling to room temperature, the mixture was filtered through Celite, and the insoluble material was washed with ethyl acetate. The filtrate and washing solution were combined, and the mixture was washed with water and saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography (ethyl acetate:hexane=80:20) to, give tert-butyl 5-(4-iodophenyl)-2,5-diazabicyclo[2.2.1]heptane-2-carboxylate (1.34 g, yield 33%).

Workup

  1. stirringthe mixture was stirred at 90° C. overnight
  2. temperatureAfter cooling to room temperature
  3. filtrationthe mixture was filtered through Celite
  4. washthe insoluble material was washed with ethyl acetate
  5. washThe filtrate and washing solution
  6. washthe mixture was washed with water and saturated brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography (ethyl acetate:hexane=80:20) to,

Sources & evidence

ORD record
ord-f5fb3553ad824d098a002a625652098a
Source dataset
uspto-grants-2015_04
Patent number
US08999989B2

Reaction notes

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