tert-butyl (2S,5S)-5-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2-[(2-fluoro-6-nitrophenoxy)methyl]morpholine-4-carboxylate → tert-butyl (2S,5S)-2-[(2-amino-6-fluorophenoxy)methyl]-5-({[tert-butyl(dimethyl)silyl]oxy}methyl)morpholine-4-carboxylate

HRID 629744Notes

Reaction equation

HRID 629744 reaction equation
[Si:1]([O:8][CH2:9][C@H:10]1[N:15]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:14][C@@H:13]([CH2:23][O:24][C:25]2[C:30]([N+:31]([O-])=O)=[CH:29][CH:28]=[CH:27][C:26]=2[F:34])[O:12][CH2:11]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H][H]>C(OCC)(=O)C.[Pd]>[NH2:31][C:30]1[CH:29]=[CH:28][CH:27]=[C:26]([F:34])[C:25]=1[O:24][CH2:23][C@H:13]1[O:12][CH2:11][C@@H:10]([CH2:9][O:8][Si:1]([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2])[N:15]([C:16]([O:18][C:19]([CH3:20])([CH3:21])[CH3:22])=[O:17])[CH2:14]1

Participants

5

Reactant 2

HCID 86726343tert-butyl (2S,5S)-5-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2-[(2-fluoro-6-nitrophenoxy)methyl]morpholine-4-carboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 86726344tert-butyl (2S,5S)-2-[(2-amino-6-fluorophenoxy)methyl]-5-({[tert-butyl(dimethyl)silyl]oxy}methyl)morpholine-4-carboxylateYield 100%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Dissolved tert-butyl (2S,5S)-5-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2-[(2-fluoro-6-nitrophenoxy)methyl]morpholine-4-carboxylate (1.68 g, 3.36 mmol) in ethyl acetate (11.19 mL) and to this solution, carefully added 10% Pd/C (0.714 g, 0.671 mmol). A hydrogen filled balloon was attached and the contents were evacuated and backfilled with H2 several times. Stirred at room temperature for 4 hours. Complete at this time by LC/MS. The solids were filtered off through a pad of celite and washed with ethyl acetate and ethanol. The contents were concentrated and then purified on silica gel (40 g) eluting with a gradient of 0-90% EtOAc/hexanes afforded the title compound (1.57 g, 3.34 mmol, 100% yield) as a yellow oil,

Workup

  1. customthe contents were evacuated
  2. filtrationThe solids were filtered off through a pad of celite
  3. washwashed with ethyl acetate and ethanol
  4. concentrationThe contents were concentrated
  5. custompurified on silica gel (40 g)
  6. washeluting with a gradient of 0-90% EtOAc/hexanes

Sources & evidence

ORD record
ord-cb7e6f31ffa444cfad91d75ff54f1c8b
Source dataset
uspto-grants-2016_04
Patent number
US09315475B2

Reaction notes

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