Benzyl Bromide → HCID 68669637, compound

HRID 1161949Notes

Reaction equation

HRID 1161949 reaction equation
[CH2:1]([N:5]1[CH2:10][CH2:9][N:8]([CH2:11][C:12]([O:14][CH3:15])=[O:13])[C:7](=[O:16])[C:6]1=[O:17])[CH2:2][CH2:3][CH3:4].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:28](Br)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>C1COCC1>[CH2:1]([N:5]1[CH2:10][CH2:9][N:8]([CH:11]([CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:12]([O:14][CH3:15])=[O:13])[C:7](=[O:16])[C:6]1=[O:17])[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 2733832Lithium HexamethyldisilazideHCID 59519985HCID 59519985, compound2×

Product 1

HCID 68669637HCID 68669637, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of methyl 2-(4-butyl-2,3-dioxopiperazin-1-yl)acetate (Intermediate E, 270 mg, 1.1 mmol) in 10 mL THF, cooled to −78° C., was added lithium bis(trimethylsilyl)amide (1M solution in THF, 1.3 mL, 1.3 mmol) dropwise. The reaction was stirred at −78° C. for 30 min and benzyl bromide (0.33 mL, 2.75 mmol) was added. The mixture was allowed to warm to rt over 2.5 h, quenched with saturated NH4Cl solution and extracted with EtOAc. The combined organic layers were washed with brine, dried and concentrated. Flash chromatography (silica gel, 50-100% EtOAc/hexanes) gave methyl 2-(4-butyl-2,3-dioxopiperazin-1-yl)-3-phenylpropanoate. 1H NMR (CDCl3) δ 7.26 (m, 5H), 5.35 (X of ABX, 1H, J=11 Hz, J=5.6 Hz), 3.76 (s, 3H), 3.47-3.34 (m, 6H), 3.12 (m, 2H), 1.49 (m, 2H), 1.27 (m, 2H), 0.90 (t, 3H, J=7.3 Hz).

Workup

  1. temperatureto warm to rt over 2.5 h
  2. customquenched with saturated NH4Cl solution
  3. extractionextracted with EtOAc
  4. washThe combined organic layers were washed with brine
  5. customdried
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-775a3e0776e843808aa9a4323351c493
Source dataset
uspto-grants-2010_10
Patent number
US07820674B2

Reaction notes

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