Chlorotrimethylsilane → HCID 90419034, compound

HRID 2202398Notes

Reaction equation

HRID 2202398 reaction equation
BrC(Br)C.C[Si](Cl)(C)C.[CH2:10]([O:12][C:13](=[O:16])[CH2:14]Br)C.[O:17]=[C:18]1[CH2:23][CH2:22][N:21]([C:24]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[O:25])[CH2:20][CH2:19]1>C1COCC1.[Zn]>[OH:17][C:18]1([CH2:14][C:13]([O:12][CH3:10])=[O:16])[CH2:19][CH2:20][N:21]([C:24]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[O:25])[CH2:22][CH2:23]1

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 7748Ethyl bromoacetateHCID 112011,1-DibromoethaneHCID 643496Benzyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 90419034HCID 90419034, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
60 °C

Procedure

To a round-bottom flask containing Zn dust (2.3 g, 36 mmol) was added dibromoethane (585 mg, 3.11 mmol). The resulting mixture was warmed to 60° C. and allowed to cool for 1 min. This heating-cooling process was repeated three more times, and then the flask was allowed to cool for an additional 3 min. Trimethylsilylchloride (456 mg, 4.2 mmol) in THF (5 mL) was added, followed by addition of ethyl-2-bromoacetate (2 g, 12 mmol) in THF (8 mL). The reaction was warmed to 60° C. for an additional two hours until a dark grey suspension was obtained. The mixture was cooled to room temperature; benzyl 4-oxopiperidine-1-carboxylate (1.9 g, 8.2 mmol) in THF (20 mL) was then added. The resulting mixture was stirred for 3 days, and then quenched with water. The solid was filtered off, and the aqueous was extracted with ethyl acetate. The combined organic layers were washed with brine and dried over Na2SO4. Purification by a standard method gave the desired product. 1H NMR (CHLOROFORM-d) δ: 7.33-7.43 (m, 5H), 5.14 (s, 2H), 3.89-4.05 (m, 2H), 3.68-3.79 (m, 3H), 3.22-3.36 (m, 2H), 2.49 (s, 2H), 2.19 (s, 1H), 1.71 (d, J=12.6 Hz, 2H), 1.53 (dd, J=12.5, 4.2 Hz, 2H). LCMS (m/z): 308.1 (M+1)+

Workup

  1. temperatureto cool for 1 min
  2. temperatureto cool for an additional 3 min
  3. temperatureThe reaction was warmed to 60° C. for an additional two hours until a dark grey suspension
  4. customwas obtained
  5. temperatureThe mixture was cooled to room temperature
  6. customquenched with water
  7. filtrationThe solid was filtered off
  8. extractionthe aqueous was extracted with ethyl acetate
  9. washThe combined organic layers were washed with brine
  10. dry with materialdried over Na2SO4
  11. customPurification by a standard method

Sources & evidence

ORD record
ord-e5899c97b08c48e2b046731a5d354555
Source dataset
uspto-grants-2016_06
Patent number
US09365545B2

Reaction notes

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