Ammonium formate → Tert-butyl 3-[(2r)-2-(aminomethyl)-3.4-dihydro-2h-chromen-6-yl]propanoate

HRID 47669Notes

Reaction equation

HRID 47669 reaction equation
C(OC([NH:11][CH2:12][C@H:13]1[CH2:22][CH2:21][C:20]2[C:15](=[CH:16][CH:17]=[C:18](/[CH:23]=[CH:24]/[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH:19]=2)[O:14]1)=O)C1C=CC=CC=1.C([O-])=O.[NH4+]>C(O)C.[OH-].[Na+].[OH-].[OH-].[Pd+2]>[NH2:11][CH2:12][C@H:13]1[CH2:22][CH2:21][C:20]2[C:15](=[CH:16][CH:17]=[C:18]([CH2:23][CH2:24][C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH:19]=2)[O:14]1

Participants

6

Reactant 2

HCID 2723923Ammonium formateHCID 10202537HCID 10202537, compound

Product 1

HCID 9943902Tert-butyl 3-[(2r)-2-(aminomethyl)-3.4-dihydro-2h-chromen-6-yl]propanoate

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 702EthanolSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of carbamate of Example 12 (10.8 g, 23.6 mmol), ammonium formate (29 g, 460 mmol) and palladium hydroxide on carbon (Pearlman's catalyst) (4.3 g) in absolute ethanol (250 mL) was heated at 50° C. for 4 hours under argon. Some white solid appeared in the condenser. The reaction mixture was vacuum filtered through a pad of Celite. The filtrate was concentrated in vacuo to obtain an off-white solid which was subsequently dissolved in 1 N sodium hydroxide solution (200 mL). The mixture was extracted with ethyl acetate (200, 200, 100 mL). The combined organic layer was washed with brine (100 mL) and dried over anhydrous sodium sulfate. Removal of solvent in vacuo afforded the desired product cleanly as an oil (6.0 g, 88%): 1H NMR (CDCl3) δ1.40 (s, 9H), 1.70-1.81 (m, 1H), 1.90-2.00 (m, 1H), 2.46-2.51 (t, J=6.9 Hz, 2H), 2.70-2.85 (m, 4H), 2.93 (d, J=5.4 Hz, 2H), 3.90-4.00 (m, 1H), 6.73 (d, J=8.4 Hz, 1H), 6.87 (s, 1H), 6.90 (d, J=8.1 Hz, 1H); CI-MS m/z 292 (M+H+).

Workup

  1. filtrationfiltered through a pad of Celite
  2. concentrationThe filtrate was concentrated in vacuo
  3. customto obtain an off-white solid which
  4. extractionThe mixture was extracted with ethyl acetate (200, 200, 100 mL)
  5. washThe combined organic layer was washed with brine (100 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. customRemoval of solvent in vacuo

Sources & evidence

ORD record
ord-0617f8ca22644349b1dc0c671c2bd3bb
Source dataset
uspto-grants-2004_03
Patent number
US06699860B2

Reaction notes

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