Boron trifluoride etherate → 1-tert-Butyl 4-ethyl 5-oxoazepane-1,4-dicarboxylate

HRID 1186109Notes

Reaction equation

HRID 1186109 reaction equation
[C:1]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].B(F)(F)F.CCOCC.[N+](=[CH:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])=[N-]>CCOCC.C([O-])([O-])=O.[Na+].[Na+].O>[CH2:30]([O:29][C:27]([CH:26]1[C:11](=[O:14])[CH2:10][CH2:9][N:8]([C:1]([O:3][C:4]([CH3:5])([CH3:7])[CH3:6])=[O:2])[CH2:13][CH2:12]1)=[O:28])[CH3:31]

Participants

7

Reactant 3

HCID 8000Boron trifluoride etherateHCID 12192Ethyl diazoacetateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 44365701-tert-Butyl 4-ethyl 5-oxoazepane-1,4-dicarboxylateYield 98%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. solution of 1-BOC-4-piperidone (20 g, 0.10 mol) in Et2O (200 mL) was added BF3.Et2O (14 mL, 0.11 mol) followed by drop-wise addition of ethyl diazoacetate (13.7 mL, 0.11 mol) over 1 h. After addition was complete, the mixture was stirred at 0° C. for 1 h. The mixture was diluted with 30% aq. Na2CO3 and water at 0° C. and extracted with EtOAc. The combined organic layers were dried (Na2SO4) and concentrated. Purification of the residue (FCC) afforded the title compound (25.6 g, 98%). 1H NMR (CDCl3): 4.25-2.03 (m, 11H), 1.47-1.45 (d, J=7.8 Hz, 9H), 1.31-1.24 (m, 3H).

Workup

  1. additionAfter addition
  2. extractionextracted with EtOAc
  3. dry with materialThe combined organic layers were dried (Na2SO4)
  4. concentrationconcentrated
  5. customPurification of the residue (FCC)

Sources & evidence

ORD record
ord-28828ee64c214a4e8c027c91cac9c036
Source dataset
uspto-grants-2014_03
Patent number
US08673895B2

Reaction notes

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