Ethylene → HCID 53709387, compound

HRID 428318Notes

Reaction equation

HRID 428318 reaction equation
[CH:1]([N:4]([CH:29]([CH3:31])[CH3:30])[CH2:5][CH2:6][C@H:7]([C:14]1[CH:19]=[C:18](Br)[CH:17]=[CH:16][C:15]=1[O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([CH3:3])[CH3:2].[C:32]1(C)C=CC=C[C:33]=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CCCC)CCCC)CCC.C=C>CC(N(C)C)=O.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH:1]([N:4]([CH:29]([CH3:31])[CH3:30])[CH2:5][CH2:6][C@H:7]([C:14]1[CH:19]=[C:18]([CH:32]=[CH2:33])[CH:17]=[CH:16][C:15]=1[O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 6325EthyleneHCID 7622TributylamineHCID 80271Tri-o-tolylphosphineHCID 12972416HCID 12972416, compound

Product 1

HCID 53709387HCID 53709387, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of (S)-N,N-diisopropyl-3-(2-benzyloxy-5-bromophenyl)-3-phenylpropanamine (prepared as described in WO 94/11337, Example 1) (8 g, 12.7 mmol), Pd(OAc)2 (28 mg, 0.12 mmol), tri-o-tolyl-phosphine (74 mg, 0.14 mmol) and tributylamine (5.9 mL, 24.5 mmol) in dimethylacetamide (50 mL) was heated to 60° C. under nitrogen atmosphere. Ethene (g) was then added to 8 bars pressure. After stirring overnight the reaction mixture was allowed to cool to room temperature. Nitrogen was flushed through the reaction vessel, and toluene and water were added. The aqueous layer was extracted with toluene and the combined organic layers were dried (MgSO4) and concentrated. The residue was treated with sodium hydroxide (1 M) and extracted with diethyl ether and toluene. The organic layer was dried (MgSO4) and concentrated in vacuo. The residue was chromatographed on silica (gradient ethyl acetate-methanol 90:10 up to 0.06% NH3 in ethyl acetate-methanol 90:10) Yield 1 g (18%); 1H NMR (CDCl3) δ0.94 (d, 12H), 2.20 (br, 2H), 2.37 (br, 2H), 3.0 (br, 2H), 4.38 (t, 1H), 5.0 (s, 2H), 5.11 (d, 1H), 5.61 (d, 1H), 6.60-6.70 (m, 1H), 6.80 (d, 1H), 7.12-7.19 (m, 12H).

Workup

  1. temperatureto cool to room temperature
  2. customNitrogen was flushed through the reaction vessel, and toluene and water
  3. additionwere added
  4. extractionThe aqueous layer was extracted with toluene
  5. dry with materialthe combined organic layers were dried (MgSO4)
  6. concentrationconcentrated
  7. additionThe residue was treated with sodium hydroxide (1 M)
  8. extractionextracted with diethyl ether and toluene
  9. dry with materialThe organic layer was dried (MgSO4)
  10. concentrationconcentrated in vacuo
  11. customThe residue was chromatographed on silica (gradient ethyl acetate-methanol 90:10 up to 0.06% NH3 in ethyl acetate-methanol 90:10) Yield 1 g (18%)

Sources & evidence

ORD record
ord-23ff211884d14fe69b7909e2e57a0105
Source dataset
uspto-grants-2001_11
Patent number
US06313132B1

Reaction notes

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