Tert-butyl 6-oxa-7-azabicyclo[3.2.2]non-8-ene-7-carboxylate → tert-butyl N-[(1S,4R)-4-hydroxycycloheptyl]carbamate

HRID 1631450Notes

Reaction equation

HRID 1631450 reaction equation
[CH:1]12[CH:16]=[CH:15][CH:5]([O:6][N:7]1[C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3][CH2:2]2.[H][H]>[Ni]>[OH:6][C@@H:5]1[CH2:4][CH2:3][CH2:2][C@H:1]([NH:7][C:8](=[O:9])[O:10][C:11]([CH3:13])([CH3:12])[CH3:14])[CH2:16][CH2:15]1

Participants

4

Reactant 2

HCID 21582700Tert-butyl 6-oxa-7-azabicyclo[3.2.2]non-8-ene-7-carboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 69723966tert-butyl N-[(1S,4R)-4-hydroxycycloheptyl]carbamate

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

A Parr bottle was charged with Raney Nickel (ca. 1 g). The catalyst was washed with ethanol and suspended in ethanol (30 mL). The starting material, 23A (1.0 g, 4.44 mmol) was added and the reaction pressurized with hydrogen. After hours, TLC analysis suggests good conversion to desired product. The reaction was flushed with nitrogen and filtered through a pad of magnesium sulfate. The filter cake was rinsed well with ethanol. The ethanol solution was evaporated. The isolated material was dissolved in tetrahydrofuran to give a cloudy solution. The liquid was passed through a PTFE filter and then evaporated. The crude product was crystallized from ether-hexanes. The crystalline material was filtered off and rinsed with hexanes. Residual solvent was removed under vacuum to give 23B (780 mg, 3.40 mmol, 77% yield) as a colorless solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 6.76 (d, 1H, J=7.6 Hz); 4.36 (d, 1H, J=4.0 Hz); 3.51-3.73 (m, 1H); 3.37 (br. s, 1H); 1.69-1.91 (m, 2H); 1.45-1.66 (m, 5H); 1.37 (s, 9H); 1.06-1.34 (m, 3H).

Workup

  1. washThe catalyst was washed with ethanol
  2. waitAfter hours

Sources & evidence

ORD record
ord-0ef491cd6c064854b500da72d24b94c8
Source dataset
uspto-grants-2014_07
Patent number
US08791257B2

Reaction notes

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