HCID 90697348, compound → HCID 91402191, compound

HRID 2416996Notes

Reaction equation

HRID 2416996 reaction equation
[CH2:1]1[CH:9]2[CH:4]([CH:5]3[CH2:10][CH:8]2[CH2:7][CH:6]3[NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH:3]=[CH:2]1.C1C2C(C3CC2CC3NC(=O)[O:31]C(C)(C)C)CC=1>C1(C)C=CC=CC=1>[OH:31][CH:2]1[CH2:3][CH:4]2[CH:9]([CH:8]3[CH2:10][CH:5]2[CH:6]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:15])([CH3:17])[CH3:16])[CH2:7]3)[CH2:1]1

Participants

4

Reactant 2

HCID 90697348HCID 90697348, compoundHCID 90889980HCID 90889980, compound

Product 1

HCID 91402191HCID 91402191, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent3×

Procedure

4.87 g of a mixture of tert-butyl (3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-5-yl)carbamate and tert-butyl (3a,4,5,6,7,7a-hexahydro-3H-4,7-methanoinden-5-yl)carbamate were dissolved in 30 ml of toluene (anhydrous) and, at RT, 20 ml of a 2 M solution of borane/dimethyl sulfide complex in toluene were added using a syringe. The mixture was stirred at RT for 24 hours, a further 10 ml of a 2 M solution of borane/dimethyl sulfide complex in toluene were added using a syringe, and the mixture was stirred at RT for another 6 hours. The volatile components were then removed under reduced pressure, 200 ml of CH2Cl2 and 33 ml of a 3 N aqueous NaOH solution were added, and the mixture was slowly admixed with 7 ml of a 30% strength aqueous H2O2 solution. The mixture was stirred at RT for 10 minutes, and a further 100 ml of a 3 N aqueous NaOH solution and 20 ml of a 30% strength aqueous H2O2 solution were added. The reaction mixture was stirred at RT for another 10 minutes and then extracted three times with, in each case, 200 ml of CH2Cl2. The extracts were dried over MgSO4 and the solvent was removed under reduced pressure. Chromatography over silica gel using MTB gave 2.9 g of an amorphous solid which was still contaminated by regioisomers.

Workup

  1. stirringthe mixture was stirred at RT for another 6 hours
  2. customThe volatile components were then removed under reduced pressure, 200 ml of CH2Cl2 and 33 ml of a 3 N aqueous NaOH solution
  3. additionwere added
  4. stirringThe mixture was stirred at RT for 10 minutes
  5. additiona further 100 ml of a 3 N aqueous NaOH solution and 20 ml of a 30% strength aqueous H2O2 solution were added
  6. stirringThe reaction mixture was stirred at RT for another 10 minutes
  7. extractionextracted three times with, in each case, 200 ml of CH2Cl2
  8. dry with materialThe extracts were dried over MgSO4
  9. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-9b23eed022c245faaf6cddd1a4f85e63
Source dataset
uspto-grants-2004_11
Patent number
US06825231B2

Reaction notes

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