3-[4-Methyl-3-oxo-7-(1-trifluoromethyl-vinyl)-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino]-azetidine-1-carboxylic acid tert-butyl ester → 3-[4-Methyl-3-oxo-7-(2,2,2-trifluoro-1-methyl-ethyl)-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino]-azetidine-1-carboxylic acid tert-butyl ester

HRID 519087Notes

Reaction equation

HRID 519087 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([NH:12][C:13]2[CH:14]=[C:15]3[C:24](=[CH:25][C:26]=2[C:27]([C:29]([F:32])([F:31])[F:30])=[CH2:28])[O:23][CH2:22][C:21]2[N:16]3[CH:17]([CH3:34])[C:18](=[O:33])[NH:19][N:20]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>CCOC(C)=O.[Pd]>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH:10]([NH:12][C:13]2[CH:14]=[C:15]3[C:24](=[CH:25][C:26]=2[CH:27]([CH3:28])[C:29]([F:31])([F:30])[F:32])[O:23][CH2:22][C:21]2[N:16]3[CH:17]([CH3:34])[C:18](=[O:33])[NH:19][N:20]=2)[CH2:11]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 1

HCID 867274573-[4-Methyl-3-oxo-7-(1-trifluoromethyl-vinyl)-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino]-azetidine-1-carboxylic acid tert-butyl ester

Product 1

HCID 867274583-[4-Methyl-3-oxo-7-(2,2,2-trifluoro-1-methyl-ethyl)-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino]-azetidine-1-carboxylic acid tert-butyl esterYield 17%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 3-[4-methyl-3-oxo-7-(1-trifluoromethyl-vinyl)-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino]-azetidine-1-carboxylic acid tert-butyl ester (0.12 g, 0.25 mmol) and Pd/C (10%, 0.10 g, 0.1 mmol) in EtOAc (60 mL) was stirred under an atmosphere of H2 (40 psi) overnight. The mixture was filtered and the filtrate was concentrated in vacuo to give a residue which was purified by preparative TLC (eluting with 50% EtOAc in petroleum ether) to give 3-[4-methyl-3-oxo-7-(2,2,2-trifluoro-1-methyl-ethyl)-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino]-azetidine-1-carboxylic acid tert-butyl ester (0.020 g, 17%). 1H NMR (CDCl3, 400 MHz): δ 8.62 (brs, 1H), 7.29 (s, 1H), 6.97 (s, 1H), 6.97 (s, 1H), 4.72 (m, 1H), 4.53 (m, 2H), 4.33 (m, 2H), 4.11 (m, 1H), 3.77 (m, 2H), 3.63 (m, 1H), 1.50 (m, 15H).

Workup

  1. filtrationThe mixture was filtered
  2. concentrationthe filtrate was concentrated in vacuo
  3. customto give a residue which
  4. customwas purified by preparative TLC (eluting with 50% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-77dfa30a5d264e6fac9df0b8dc7898cd
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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