1,1-Dimethylethyl (3S)-3-(azidomethyl)-3-fluoro-1-piperidinecarboxylate → tert-Butyl (R)-3-(aminomethyl)-3-fluoropiperidine-1-carboxylate

HRID 473315Notes

Reaction equation

HRID 473315 reaction equation
[N:1]([CH2:4][C@:5]1([F:18])[CH2:10][CH2:9][CH2:8][N:7]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:6]1)=[N+]=[N-]>C(O)C.[Pd]>[NH2:1][CH2:4][C@:5]1([F:18])[CH2:10][CH2:9][CH2:8][N:7]([C:11]([O:13][C:14]([CH3:16])([CH3:15])[CH3:17])=[O:12])[CH2:6]1

Participants

4

Reactant 1

HCID 866768001,1-Dimethylethyl (3S)-3-(azidomethyl)-3-fluoro-1-piperidinecarboxylate

Product 1

HCID 68210002tert-Butyl (R)-3-(aminomethyl)-3-fluoropiperidine-1-carboxylateYield 101.3%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

1,1-Dimethylethyl (3S)-3-(azidomethyl)-3-fluoro-1-piperidinecarboxylate (36 g, 139 mmol) was dissolved in ethanol (500 ml) and added under nitrogen to Pd/C (2.6 g, 1.222 mmol). The mixture was hydrogenated at atmospheric pressure overnight. The suspension was filtered and the filtrate evaporated in vacuo to give 1,1-dimethylethyl (3R)-3-(aminomethyl)-3-fluoro-1-piperidinecarboxylate as a pale yellow oil (32.7 g). 1H NMR (CDCl3) 3.75-3.52 ppm (2H, 2×m, 2×CH), 3.30 ppm (1H, dd, CH), 3.20 ppm (1H, m, CH), 2.90-2.73 ppm (2H, m, CH2), 1.96-1.72 ppm (2H, 2×m, CH2), 1.70-1.58 ppm (1H, m, CH), 1.57-1.43 ppm (10H, m+s, CH+3×CH3), 1.32 ppm (2H, br.s, NH2).

Workup

  1. customwas hydrogenated at atmospheric pressure overnight
  2. filtrationThe suspension was filtered
  3. customthe filtrate evaporated in vacuo

Sources & evidence

ORD record
ord-6b78589fb10e40deb88ac399d5798f51
Source dataset
uspto-grants-2014_01
Patent number
US08633319B2

Reaction notes

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