Benzyl chloroformate → HCID 86597993, compound

HRID 2116436Notes

Reaction equation

HRID 2116436 reaction equation
C(=O)(O)[O-].[K+].C(OC(Cl)=O)C1C=CC=CC=1.[CH2:17]([O:24][C:25]([N:27]1[C@@H:35]2[C@@H:30]([CH2:31][CH2:32][CH2:33][CH2:34]2)[CH2:29][C@H:28]1[C:36]([O:38][CH2:39][CH3:40])=[O:37])=[O:26])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C(ON1[C@H]2[C@H](CCCC2)C(=C=O)[C@@H]1C(OCC)=O)C1C=CC=CC=1>C(OCC)(=O)C.O>[CH2:17]([O:24][C:25]([N:27]1[C@H:35]2[C@H:30]([CH2:31][CH2:32][CH2:33][CH2:34]2)[CH2:29][C@@H:28]1[C:36]([O:38][CH2:39][CH3:40])=[O:37])=[O:26])[C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

Participants

7

Reactant 4

HCID 10387Benzyl chloroformateHCID 516893Potassium BicarbonateHCID 86597994HCID 86597994, compound2×HCID 86597995HCID 86597995, compound

Product 1

HCID 86597993HCID 86597993, compoundYield 88.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
0 °C

Procedure

In 38.8 g of ethyl acetate was dissolved 15.6 g (78.0 mmol) of the mixture of the enantiomers obtained in Reference Example 1. To the resulting solution were added 38.8 g of water and 15.5 g of potassium bicarbonate and mixed. To this solution cooled to 0° C. was dropped 15.0 g of benzyloxycarbonyl chloride over 1 hour. After the completion of dropping, the solution was raised to room temperature, and then agitated at room temperature for 4 hours to complete the reaction. After the completion of reaction, to the reaction mixture was added 40 g of ethyl acetate to separate the resultant solution. From the resulting organic phase the solvent was removed by distillation to obtain an oily mixture of ethyl (2S, 3aS, 7aS)-N-benzyloxycarbonyl-octahydro-1H-indole-2-carboxylate and ethyl (2R, 3aR, 7aR)-N-benzyloxy-carbonyl-octahydro-1H-indole-2-carboxylate. This oily mixture was purified using n-hexane/ethyl acetate (eluate of the volume ratio of 85:15) by silica gel column chromatography to yield 24.3 g of a mixture of ethyl (2S, 3aS, 7aS)-N-benzyloxycarbonyl-octahydro-1H-indole-2-carboxylate and ethyl (2R, 3aR, 7aR)-N-benzyloxycarbonyl-octahydro-1H-indole-2-carboxylate [contained pure compounds were 22.8 g, 68.8 mmol (yield 88.2%)].

Workup

  1. customobtained in Reference Example 1
  2. additionmixed
  3. temperaturethe solution was raised to room temperature
  4. customthe reaction
  5. customAfter the completion of reaction
  6. customto separate the resultant solution
  7. customFrom the resulting organic phase the solvent was removed by distillation
  8. customto obtain
  9. customThis oily mixture was purified

Sources & evidence

ORD record
ord-0db95290a3f240dbb07b64dac345bb7b
Source dataset
uspto-grants-2008_10
Patent number
US07439036B2

Reaction notes

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