Benzyl chloroformate → HCID 67057884, compound

HRID 2361703Notes

Reaction equation

HRID 2361703 reaction equation
[N:1]1([C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[O:14])[CH2:7][CH2:6][CH:5]=[C:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:3][CH2:2]1.CCN(C(C)C)C(C)C.ClC(OCC1C=CC=CC=1)=O>C1COCC1.ClCCl.[Pd]>[N:1]1([C:13]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)=[O:14])[CH2:7][CH2:6][CH2:5][CH:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:3][CH2:2]1

Participants

7

Reactant 3

HCID 10387Benzyl chloroformateHCID 81531DiisopropylethylamineHCID 67057891HCID 67057891, compound

Product 1

HCID 67057884HCID 67057884, compoundYield 59%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 1-benzyl 4-ethyl 2,3,6,7-tetrahydro-1H-azepine-1,4-dicarboxylate (890 mg, 2.93 mmol) and 5% Pd/C (90 mg) in THF (70 ml) were stirred under a hydrogen atmosphere for 12 hours. The mixture was then filtered over celite and concentrated giving colourless oil. This was dissolved in dichloromethane (10 ml), cooled to 0° C. and DIPEA (1.02 ml, 5.86 mmol) followed by benzyl chloroformate (0.45 ml, 3.22 mmol) were added. On complete addition the reaction was raised to room temperature and stirred for a further 1 hour. The mixture was then diluted with dichloromethane (40 ml) and washed with water (2×20 ml), dried (MgSO4), filtered and concentrated. The residue was purified by silica FCC (using a gradient of eluents; 99:1 to 90:10 dichloromethane/MeOH) to give the title product as colourless oil (521 mg, 59%).

Workup

  1. filtrationThe mixture was then filtered over celite
  2. concentrationconcentrated
  3. customgiving colourless oil
  4. additionwere added
  5. additionOn complete addition the reaction
  6. temperaturewas raised to room temperature
  7. washwashed with water (2×20 ml)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by silica FCC (

Sources & evidence

ORD record
ord-9abf8c10ebda4ffb9325bf3b1d5bdb12
Source dataset
uspto-grants-2014_04
Patent number
US08691804B2

Reaction notes

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