Methanol → rac-methyl (1R,2R)-2-(4-aminophenyl)cyclopropane-1-carboxylate

HRID 922193Notes

Reaction equation

HRID 922193 reaction equation
CO.[N+:3]([C:6]1[CH:11]=[CH:10][C:9]([C@@H:12]2[CH2:14][C@H:13]2[C:15]([O:17][CH3:18])=[O:16])=[CH:8][CH:7]=1)([O-])=O>C(OCC)(=O)C.[Pd]>[NH2:3][C:6]1[CH:7]=[CH:8][C:9]([C@@H:12]2[CH2:14][C@H:13]2[C:15]([O:17][CH3:18])=[O:16])=[CH:10][CH:11]=1

Participants

5

Reactant 2

HCID 887MethanolHCID 11736165Methyl (1R,2R)-2-(4-nitrophenyl)cyclopropanecarboxylate

Product 1

HCID 68667437rac-methyl (1R,2R)-2-(4-aminophenyl)cyclopropane-1-carboxylateYield 33.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent2×

Procedure

To a 1000 mL parr hydrogenater flask with methanol (70 mL) and ethyl acetate (70 mL), was added methyl (1R,2R)-2-(4-nitrophenyl)cyclo propane carboxylate (14 g, 63.3 mmol) and 10% Pd/C (2 g) under N2 atmosphere. The RM was hydrogenated at 40 psi for 5 h. RM was diluted with ethyl acetate (100 mL), filtered through celite bed to remove Pd/C and evaporated to dryness under reduced pressure. The crude was purified by flash column chromatography on silica gel (230/400 mesh), to give the product (4 g, yield: 33.1%). MS (ESI, 120 eV): m/z=192.1 (M+H)+; 1H NMR (300 MHz, CDCl3): δ 6.83-6.86 (d, 2H), 6.58-6.61 (d, 2H), 3.63 (s, 3H), 2.36-2.39 (m, 1H), 1.69-1.75 (m, 1H), 1.42-1.49 (m, 1H), 1.14-1.20 (m, 1H).

Workup

  1. filtrationfiltered through celite bed
  2. customto remove Pd/C
  3. customevaporated to dryness under reduced pressure
  4. customThe crude was purified by flash column chromatography on silica gel (230/400 mesh)

Sources & evidence

ORD record
ord-040bdabe833d4ba2831b2424bb3c1590
Source dataset
uspto-grants-2016_03
Patent number
US09278915B2

Reaction notes

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