Potassium Permanganate → tert-Butyl ((S)-1-amino-3-((R)-tetrahydro-2H-pyran-3-yl)propan-2-yl)(methyl)carbamate

HRID 218432Notes

Reaction equation

HRID 218432 reaction equation
[C:1]([C@@H:3]([N:11]([CH3:19])[C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:4][C@H:5]1[CH2:10][CH2:9][CH2:8][O:7][CH2:6]1)#[N:2].CO.C(Cl)Cl.[O-][Mn](=O)(=O)=O.[K+]>N.CO.[Ni]>[NH2:2][CH2:1][C@@H:3]([N:11]([CH3:19])[C:12](=[O:18])[O:13][C:14]([CH3:15])([CH3:17])[CH3:16])[CH2:4][C@H:5]1[CH2:10][CH2:9][CH2:8][O:7][CH2:6]1

Participants

7

Reactant 3

HCID 516875Potassium PermanganateHCID 21226129Dichloromethane methanolHCID 58011538tert-butyl (S)-1-cyano-2-((R)-tetrahydro-2H-pyran-3-yl)ethyl(methyl)carbamate

Product 1

HCID 58011482tert-Butyl ((S)-1-amino-3-((R)-tetrahydro-2H-pyran-3-yl)propan-2-yl)(methyl)carbamateYield 92%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 222AmmoniaSolventHCID 887MethanolSolvent

Procedure

tert-Butyl (S)-1-cyano-2-((R)-tetrahydro-2H-pyran-3-yl)ethyl(methyl)carbamate (397 mg, 4:1 mixture of diastereomers at the alpha-amino stereocenter) was dissolved in a solution of 4M NH3 in MeOH (15 mL) and passed through a Raney-nickel cartridge (CatCart®, 50 mm) on an in-line hydrogenation apparatus (H-Cube) with the following settings: ambient temperature (14° C.), flow rate 1.0 mL/min, H2 pressure 30 atm. The solution was recirculated so that the product solution was fed back into the apparatus. After thirty minutes, TLC analysis (1:9 MeOH/CH2Cl2, KMnO4 stain) showed complete conversion of the starting material. After 60 min total reaction time, the solution was evaporated to yield 371 mg (92%) of tert-butyl (S)-1-amino-3-((R)-tetrahydro-2H-pyran-3-yl)propan-2-yl(methyl)carbamate as a clear, rose-colored oil. LC-MS (ELSD) m/e 273.6 (M+H)+.

Workup

  1. customambient temperature (14° C.), flow rate 1.0 mL/min, H2 pressure 30 atm
  2. waitAfter thirty minutes
  3. customthe solution was evaporated

Sources & evidence

ORD record
ord-de6209de854f46178d4cc2c018a10d23
Source dataset
uspto-grants-2012_06
Patent number
US08198453B2

Reaction notes

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