Chlorotrimethylsilane → 1776065-88-3

HRID 1051591Notes

Reaction equation

HRID 1051591 reaction equation
BrCCBr.Cl[Si](C)(C)C.I[CH:11]1[CH2:14][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12]1.Br[C:23]1[S:24][CH:25]=[C:26]([Br:28])[N:27]=1>O1CCCC1.[Zn].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].O>[Br:28][C:26]1[N:27]=[C:23]([CH:11]2[CH2:14][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12]2)[S:24][CH:25]=1

Participants

9

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 27632972,4-Dibromo-1,3-thiazoleHCID 11000522Tert-butyl 3-iodoazetidine-1-carboxylate

Product 1

HCID 1180762581776065-88-3Yield 15.3%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
80 °C

Procedure

1,2-Dibromoethane (0.084 mL, 0.97 mmol) was added to a mixture of zinc powder (0.520 g, 8.13 mmol) in tetrahydrofuran (2 mL), and the resulting mixture was stirred for 10 min at 80° C. and was then cooled to room temperature. A solution of chlorotrimethylsilane (0.115 mL, 1.22 mmol) in tetrahydrofuran (1 mL) was added dropwise with stirring, and the resulting mixture stirred for 45 min at room temperature. A solution of tert-butyl 3-iodoazetidine-1-carboxylate (1.74 g, 6.15 mmol) in tetrahydrofuran (2 mL) was added, and the resulting mixture stirred for 2 h at room temperature. A solution of 2,4-dibromothiazole (0.744 g, 3.09 mmol) in tetrahydrofuran (1 mL) and tetrakis(triphenylphosphine)palladium(O) (0.354 g, 0.31 mmol) were added, and the resulting mixture stirred overnight at room temperature. The reaction mixture was poured into water (10 mL) and extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue was purified via column chromatography on silica gel (eluting with 1:2, ethyl acetate/petroleum ether) to afford tert-butyl 3-(4-bromothiazol-2-yl)azetidine-1-carboxylate (0.151 g, 8%) of as yellow oil. MS (ESI, pos. ion) m/z 319, 321 [M+H]+.

Workup

  1. temperaturewas then cooled to room temperature
  2. stirringwith stirring
  3. stirringthe resulting mixture stirred for 45 min at room temperature
  4. stirringthe resulting mixture stirred for 2 h at room temperature
  5. stirringthe resulting mixture stirred overnight at room temperature
  6. extractionextracted with ethyl acetate (3×10 mL)
  7. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum
  10. customThe residue was purified via column chromatography on silica gel (eluting with 1:2, ethyl acetate/petroleum ether)

Sources & evidence

ORD record
ord-181191102f0c44db8cb1f0510d9a0dbe
Source dataset
uspto-grants-2016_07
Patent number
US09388161B2

Reaction notes

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