Ethyl Acetoacetate → HCID 67443686, compound

HRID 1400948Notes

Reaction equation

HRID 1400948 reaction equation
[N:1]1([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.[C:14]([O:20][CH2:21][CH3:22])(=[O:19])[CH2:15][C:16]([CH3:18])=O.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C(Cl)Cl>[CH2:21]([O:20][C:14](=[O:19])[CH2:15][CH:16]([N:4]1[CH2:5][CH2:6][N:1]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:2][CH2:3]1)[CH3:18])[CH3:22]

Participants

5

Reactant 3

HCID 8868Ethyl AcetoacetateHCID 143452tert-Butyl piperazine-1-carboxylateHCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 67443686HCID 67443686, compoundYield 63.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of tert-butyl piperazine-1-carboxylate (1 g, 5.37 mmol), ethyl acetoacetate (883 μl, 6.98 mmol) in DCM (30 ml) was stirred for 30 min at rt under nitrogen, then (2.4 g, 10.74 mmol) NaBH(OAc)3 was added. The reaction mixture was stirred at rt overnight, quenched by addition of water, stirred for 15 min and slowly diluted with a saturated aqueous solution of sodium bicarbonate (pH around 8-9). The reaction mixture was shaken for 1 h. After separation, the aqueous layer was extracted with DCM. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by Biotage (Snap 50 g cartridge, MeOH/DCM: 0/100 to 5/95 over 20 CV, not UV active) to afford the desired product 513 (1.03 g, 3.43 mmol, 63% yield) as a colorless sticky oil. MS (m/z): 301.4 (M+H).

Workup

  1. customquenched by addition of water
  2. stirringstirred for 15 min
  3. additionslowly diluted with a saturated aqueous solution of sodium bicarbonate (pH around 8-9)
  4. stirringThe reaction mixture was shaken for 1 h
  5. customAfter separation
  6. extractionthe aqueous layer was extracted with DCM
  7. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was purified by Biotage (Snap 50 g cartridge, MeOH/DCM

Sources & evidence

ORD record
ord-52a1ddcbda5e411eb42af3dadc4809cb
Source dataset
uspto-grants-2014_12
Patent number
US08906852B2

Reaction notes

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