Water → 8-(1,1-Dimethylethyl) 8-azabicyclo[3.2.1]oct-2-ene-3,8-dicarboxylate

HRID 40702Notes

Reaction equation

HRID 40702 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH:13]2[CH2:14][CH2:15][CH:9]1[CH:10]=[C:11](OS(C(F)(F)F)(=O)=O)[CH2:12]2)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(N(C(C)C)CC)(C)C.[O:33]1[CH2:38]COCC1.ClCCl.[OH2:42]>CN(C)C1C=CN=CC=1.C(=[Mo](=C=O)(=C=O)(=C=O)(=C=O)=C=O)=O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:1]([O:5][C:6]([N:8]1[CH:13]2[CH2:14][CH2:15][CH:9]1[CH:10]=[C:11]([C:38]([OH:33])=[O:42])[CH2:12]2)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

10

Reactant 5

HCID 962Water2×HCID 6344DichloromethaneHCID 312751,4-DioxaneHCID 81531DiisopropylethylamineHCID 226480948-Boc-3-(trifluoromethylsulfonyloxy)-8-azabicyclo[3.2.1]oct-3-ene

Product 1

HCID 469418218-(1,1-Dimethylethyl) 8-azabicyclo[3.2.1]oct-2-ene-3,8-dicarboxylate

Reagents, catalysts & solvents 4

HCID 142844-(Dimethylamino)pyridineCatalystHCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 178521658HCID 178521658, compoundCatalyst

Conditions

Temperature
150 °C

Procedure

3-Trifluoromethanesulfonyloxy-8-azabicyclo[3.2.1]oct-2-ene-8-carboxylic acid tert-butyl ester (2.0 g, 5.6 mmol), hexacarbonylmolybdenum (0.74 g, 2.8 mmol), palladium diacetate (0.13 g, 0.56 mmol), 1,1′-bis(diphenylphosphino)ferrocene (0.31 g, 0.56 mmol), 4-dimethylaminopyridine (1.37 g, 11.2 mmol) and diisopropyl-ethylamine (2.24 ml, 12.9 mmol) are placed in 2.0 ml of water and 12 ml of dioxane in a microwave reaction vessel. The medium is microwave-heated at 150° C. for 10 min. The crude product is taken up with water and with dichloromethane. The organic phase is extracted with a saturated aqueous NaHCO3 solution. The aqueous phase is acidified with KHSO4 and then extracted with ethyl acetate. The organic phase is washed with water and then with a saturated aqueous sodium chloride solution and dried over MgSO4. After concentrating to dryness, 2.7 g of expected 8-aza-bicyclo[3.2.1]oct-2-ene-3,8-dicarboxylic acid 8-tert-butyl ester are obtained.

Workup

  1. extractionThe organic phase is extracted with a saturated aqueous NaHCO3 solution
  2. extractionextracted with ethyl acetate
  3. washThe organic phase is washed with water
  4. dry with materialwith a saturated aqueous sodium chloride solution and dried over MgSO4
  5. concentrationAfter concentrating to dryness, 2.7 g of expected 8-aza-bicyclo[3.2.1]oct-2-ene-3,8-dicarboxylic acid 8-tert-butyl ester
  6. customare obtained

Sources & evidence

ORD record
ord-7f18c8ddc6a24543aa3570c9eaa91965
Source dataset
uspto-grants-2013_09
Patent number
US08530477B2

Reaction notes

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