Chlorotrimethylsilane → HCID 68292479, compound

HRID 529473Notes

Reaction equation

HRID 529473 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](/[N:9]=[CH:10]\[C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:5][CH:4]=1.Br[CH2:17][CH:18]=[C:19]([CH3:21])[CH3:20].[Si](Cl)(C)(C)C.[NH4+].[Cl-]>[Zn].CN(C=O)C>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([NH:9][CH:10]([C:19]([CH3:21])([CH3:20])[CH:18]=[CH2:17])[C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:7][CH:8]=1

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 25517Ammonium ChlorideHCID 700922-Butene, 1-bromo-3-methyl-HCID 178472672HCID 178472672, compound

Product 1

HCID 68292479HCID 68292479, compoundYield 21%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a round bottom flask was added (Z)-ethyl 2-(4-methoxyphenylimino)acetate (4000 mg, 19.30 mmol) and DMF (30 mL). The reaction was cooled to 0° C. Then, 1-bromo-3-methylbut-2-ene (3740 mg, 25.09 mmol) was added to the reaction followed by zinc (1641 mg, 25.09 mmol) and a drop of TMS-Cl (0.247 mL, 1.93 mmol). The reaction mixture was slowly warmed up to rt over 45 min and then stirred at rt for 20 min. The reaction mixture was cooled to 0° C. and aqueous 5% NH4Cl (10 mL) was added to the reaction. The reaction was extracted with ether (3×50 mL). The combined ether layer was washed with water (100 mL) and saturated aqueous NaCl (100 mL). The organic layer was separated, dried over MgSO4, filtered and concentrated. The residue was purified using silica gel chromatography (ISCO system) eluting with a gradient of 0-60% EtOAc/Hex to give ethyl 2-(4-methoxyphenylamino)-3,3-dimethylpent-4-enoate (1.1 g, 4.0 mmol, 21% yield) as a yellow oil. 1H NMR (500 MHz, CDCl3) δ ppm 6.76 (d, J=9.35 Hz, 2H), 6.60 (d, J=8.80 Hz, 2H), 5.96 (dd, J=17.32, 10.72 Hz, 1H), 5.19-5.08 (m, 2H), 4.15 (q, 2H), 3.85 (s, 1H), 3.77-3.71 (m, 4H), 1.23 (t, J=7.15 Hz, 3H), 1.21 (s, 3H), 1.17 (s, 3H); 13C NMR (126 MHz, CDCl3) δ ppm 173.09, 152.71, 143.47, 141.42, 115.30, 114.79, 113.92, 66.02, 60.54, 55.69, 40.06, 24.89, 23.70, 14.27.

Workup

  1. temperatureThe reaction mixture was slowly warmed up to rt over 45 min
  2. temperatureThe reaction mixture was cooled to 0° C.
  3. extractionThe reaction was extracted with ether (3×50 mL)
  4. washThe combined ether layer was washed with water (100 mL) and saturated aqueous NaCl (100 mL)
  5. customThe organic layer was separated
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified
  10. washeluting with a gradient of 0-60% EtOAc/Hex

Sources & evidence

ORD record
ord-5cdc2636fac14cc080c03c031fcf1c42
Source dataset
uspto-grants-2016_05
Patent number
US09346852B2

Reaction notes

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