Tri-o-tolylphosphine → Tert-butyl 2,6-dichlorophenethyl(3-(2-oxopropyl)benzyl)carbamate

HRID 553280Notes

Reaction equation

HRID 553280 reaction equation
[C:1]([O:5][C:6](=[O:26])[N:7]([CH2:16][CH2:17][C:18]1[C:23]([Cl:24])=[CH:22][CH:21]=[CH:20][C:19]=1[Cl:25])[CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11](I)[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].C[O-].[CH2:29]([Sn+](CCCC)CCCC)[CH2:30][CH2:31]C.C(OC=CC(=C)C)(=[O:44])C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C1(C)C=CC=CC=1>[C:1]([O:5][C:6](=[O:26])[N:7]([CH2:16][CH2:17][C:18]1[C:23]([Cl:24])=[CH:22][CH:21]=[CH:20][C:19]=1[Cl:25])[CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:29][C:30](=[O:44])[CH3:31])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 80271Tri-o-tolylphosphineHCID 11964040Methoxytri-n-butylstannaneHCID 534018541-Acetoxy-3-methyl-1,3-butadieneHCID 67165818[2-(2,6-Dichloro-phenyl)-ethyl]-(3-iodo-benzyl)-carbamic acid tert-butyl ester

Product 1

HCID 67165764Tert-butyl 2,6-dichlorophenethyl(3-(2-oxopropyl)benzyl)carbamate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

[2-(2,6-Dichloro-phenyl)-ethyl]-(3-iodo-benzyl)-carbamic acid tert-butyl ester (Example 14, step b) (500 mg), tributyltin methoxide (350 μL), isoprenyl acetate (170 μL), tri-o-tolylphosphine (30 mg) and toluene (20 mL) were charged to a flask and the solution degassed with nitrogen for 5 minutes. Palladium acetate (10 mg) was added and the resultant mixture heated to 100° C., under nitrogen, for 3 hours. On cooling, potassium fluoride (580 mg) in water (3 mL) was added, stir at room temperature for 18 hours. The solids were filtered off, and the filter cake washed with ethyl acetate. The filtrate was evaporated and purified on silica, eluting with a gradient of iso-hexane/ethyl acetate [4:1 to 2:1], to give the subtitle product as an oil (230 mg).

Workup

  1. customthe solution degassed with nitrogen for 5 minutes
  2. additionPalladium acetate (10 mg) was added
  3. temperatureOn cooling
  4. additionpotassium fluoride (580 mg) in water (3 mL) was added
  5. filtrationThe solids were filtered off
  6. washthe filter cake washed with ethyl acetate
  7. customThe filtrate was evaporated
  8. custompurified on silica
  9. washeluting with a gradient of iso-hexane/ethyl acetate [4:1 to 2:1]

Sources & evidence

ORD record
ord-ad8f92d1c2294bb6a3c2dd8618b77800
Source dataset
uspto-grants-2011_05
Patent number
US07951954B2

Reaction notes

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