Benzyl Bromide → (1R,7S)-3-benzyl-1,10,10-trimethyl-4-phenyl-3,4-diazatricyclo[5.2.1.02,6]dec-2(6)-en-5-one

HRID 1437910Notes

Reaction equation

HRID 1437910 reaction equation
[CH2:1](Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[C:15]1([N:21]2[C:29](=[O:30])[C:28]3[C@@H:27]4[C:31]([CH3:33])([CH3:32])[C@@:24]([CH3:34])([CH2:25][CH2:26]4)[C:23]=3[NH:22]2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CC(C)=O.CO>[CH2:1]([N:22]1[C:23]2[C@@:24]3([CH3:34])[C:31]([CH3:33])([CH3:32])[C@H:27]([CH2:26][CH2:25]3)[C:28]=2[C:29](=[O:30])[N:21]1[C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 7498Benzyl Bromide2×HCID 11430Potassium CarbonateHCID 57941335(4s,7r)-2-Phenyl-7,8,8-trimethyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one2×

Product 1

HCID 16118895(1R,7S)-3-benzyl-1,10,10-trimethyl-4-phenyl-3,4-diazatricyclo[5.2.1.02,6]dec-2(6)-en-5-oneYield 4%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 887MethanolSolvent

Procedure

A mixture of benzyl bromide (1.54 mL, 13.0 mmol), potassium carbonate (3.58 g, 25.9 mmol), and (4S,7R)-2-phenyl-7,8,8-trimethyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (Intermediate 6; 1.74 g, 6.5 mmol) in acetone (20 mL) and methanol (3 mL) was heated at reflux overnight, then a further portion of benzyl bromide (0.75 mL, 6.3 mmol) was added and the reaction mixture was allowed to stir at room temperature over the weekend. The solvent was evaporated and the residue was partitioned between water and dichloromethane. The organic layer was evaporated and the residue was chromatographed (0-50% ethyl acetate/hexanes), and recrystallized from ethyl acetate/hexanes to give (4S,7R)-1-benzyl-7,8,8-trimethyl-2-phenyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (94 mg, 3%) as a white solid. APCI-MS (M+H) 359.

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. customThe solvent was evaporated
  4. customthe residue was partitioned between water and dichloromethane
  5. customThe organic layer was evaporated
  6. customthe residue was chromatographed (0-50% ethyl acetate/hexanes)
  7. customrecrystallized from ethyl acetate/hexanes

Sources & evidence

ORD record
ord-6945c8048d364708b9195eff016fcf95
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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