1-Bromo-4-iodobenzene → HCID 117843577, compound

HRID 2209105Notes

Reaction equation

HRID 2209105 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[CH:9]12[CH2:22][CH:13]([N:14]1[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12][NH:11][CH2:10]2.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.CC(C)([O-])C.[Na+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:11]2[CH2:12][CH:13]3[CH2:22][CH:9]([N:14]3[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:10]2)=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 115221-Bromo-4-iodobenzeneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23676156Sodium t-butoxideHCID 66676870tert-Butyl 3,6-diazabicyclo(3.1.1)heptane-6-carboxylate

Product 1

HCID 117843577HCID 117843577, compoundYield 28.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

In a 48 mL sealed tube were placed 1-bromo-4-iodobenzene (1498.3 mg, 5.30 mmol), tert-butyl 3,6-diazabicyclo[3.1.1]heptane-6-carboxylate (1000.0 mg, 5.04 mmol), Pd2(dba)3 (138.6 mg, 0.15 mmol), XantPhos (262.7 mg, 0.45 mmol), and sodium t-butoxide (1454.2 mg, 15.13 mmol) in toluene (36 ml). The reaction mixture was stirred at 60° C. for 3 h. Then it was cooled to room temperature. Then it was quenched with water and the organic layers were extracted with EtOAc (3×10 mL). The combined organic layers were washed with water (2×10 mL) and brine (1×10 mL), dried (Na2SO4), concentrated, and purified by flash chromatography (100% Hexane to 100% EtOAc) to give 500.0 mg (28%) of tert-butyl 3-(4-bromophenyl)-3,6-diazabicyclo[3.1.1]heptane-6-carboxylate.

Workup

  1. customIn a 48 mL sealed tube
  2. temperatureThen it was cooled to room temperature
  3. customThen it was quenched with water
  4. extractionthe organic layers were extracted with EtOAc (3×10 mL)
  5. washThe combined organic layers were washed with water (2×10 mL) and brine (1×10 mL)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. custompurified by flash chromatography (100% Hexane to 100% EtOAc)

Sources & evidence

ORD record
ord-5ff034bc9c954676b98ec0f8cb2f195e
Source dataset
uspto-grants-2016_06
Patent number
US09376441B2

Reaction notes

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