Ammonium formate → HCID 71138322, compound

HRID 1526420Notes

Reaction equation

HRID 1526420 reaction equation
C([O:8][C:9]1[CH:17]=[CH:16][C:15]2[N:14]3[CH2:18][CH2:19][C@H:20]([CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:13]3=[CH:12][C:11]=2[CH:10]=1)C1C=CC=CC=1.C([O-])=O.[NH4+]>CO.CC([O-])=O.CC([O-])=O.[Pd+2]>[OH:8][C:9]1[CH:17]=[CH:16][C:15]2[N:14]3[CH2:18][CH2:19][C@H:20]([CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:13]3=[CH:12][C:11]=2[CH:10]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 71138388HCID 71138388, compound

Product 1

HCID 71138322HCID 71138322, compoundYield 99%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 887MethanolSolvent

Procedure

A mixture of (R)-tert-butyl 2-(7-(benzyloxy)-2,3-dihydro-1H-pyrrolo[1,2-a]indol-1-yl)acetate (0.320 g, 0.848 mmol), Pd(OAc)2 (0.019 g, 0.085 mmol) and ammonium formate (0.214 g, 3.39 mmol) in methanol (20 mL) was heated under reflux overnight. After cooling the mixture was filtered through celite and then the solvent was removed under reduced pressure. Water (10 mL) and DCM (10 mL) were added and the 2 layers separated. The aqueous layer was extracted with DCM then the combined organics dried by passing through a phase separator cartridge. The solvent was removed under reduced pressure to give (R)-tert-butyl 2-(7-hydroxy-2,3-dihydro-1H-pyrrolo[1,2-a]indol-1-yl)acetate (0.240 g, 0.835 mmol, 99% yield, >70% ee) as a colorless oil. Exact mass calculated for C17H21NO3: 287.2, found: LCMS m/z=288.2, [M+H+]; 1H NMR (400 MHz, CDCl3) δ ppm 1.56 (s, 9 H), 3.40 (m, 2 H), 4.13 (t, J=6.6 Hz, 2 H), 5.11 (s, 2 H), 5.80 (s, 1 H), 7.00 (dd, J1=9.0, J2=2.2 Hz, 1 H), 7.18 (m, 2 H), 7.33 (m, 1 H), 7.39 (m, 2 H), 7.48 (m, 2 H), 7.55 (s, 1 H) 1H NMR (400 MHz, d6-DMSO) δ ppm 1.44 (s, 9 H), 2.18 (m, 1 H), 2.52 (dd, J1=15.9, J2=7.7 Hz, 1 H), 2.62 (dd, J1=15.9, J2=7.1 Hz, 1 H), 2.74 (m, 1 H), 3.54 (m, 1 H), 3.91 (m, 1 H), 4.05 (ddd, J1=9.8, J2=8.5 Hz, J3=4.3 Hz 1 H), 5.88 (s, 1 H), 6.54 (m, 1 H), 6.76 (d, J=2.3 Hz, 1 H), 7.06 (d, J=8.6 Hz, 1 H), 8.54 (s, 1 H).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux overnight
  3. temperatureAfter cooling the mixture
  4. filtrationwas filtered through celite
  5. customthe solvent was removed under reduced pressure
  6. additionWater (10 mL) and DCM (10 mL) were added
  7. customthe 2 layers separated
  8. extractionThe aqueous layer was extracted with DCM
  9. customthe combined organics dried
  10. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-cb9232abd53f450b8080f1c62da7530f
Source dataset
uspto-grants-2015_07
Patent number
US09085581B2

Reaction notes

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