tert-Butyl piperazine-1-carboxylate → Tert-butyl 4-(oxetan-3-YL)piperazine-1-carboxylate

HRID 633402Notes

Reaction equation

HRID 633402 reaction equation
[N:1]1([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.[O:14]1[CH2:17][C:16](=O)[CH2:15]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C([O-])(O)=O.[Na+]>ClCCCl.C(Cl)Cl>[O:14]1[CH2:17][CH:16]([N:4]2[CH2:5][CH2:6][N:1]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:2][CH2:3]2)[CH2:15]1

Participants

7

Reactant 4

HCID 143452tert-Butyl piperazine-1-carboxylateHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 150242543-Oxetanone

Product 1

HCID 59605443Tert-butyl 4-(oxetan-3-YL)piperazine-1-carboxylateYield 84%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of tert-butyl piperazine-1-carboxylate (10.8 g, 1.2 eq, 58.0 mmol) and oxetan-3-one (3.5 g, 1.0 eq, 14 mmol) in 1,2-dichloroethane (100 mL) was stirred at room temperature. Sodium triacetoxyborohydride (16.4 g, 1.6 eq, 77.3 mmol) was added in portions to the above solution and the heterogeneous mixture was stirred at room temperature overnight. The reaction mixture was diluted with CH2Cl2 (200 mL) and pardoned with aqueous saturated NaHCO3 solution (100 mL). The layers were separated and the organic layer was washed with brine solution (2×50 mL). The combined organic layers were dried over Na2SO4. Removal of the solvents and purification of the crude mixture by column chromatography on silica gel (ISCO System) using 20% MeOH in CH2Cl2/CH2Cl2 (gradient system from 0:1 to 1:9) as eluent gave tert-butyl 4-(oxetan-3-yl)piperazine-1-carboxylate in 84% yield.

Workup

  1. customThe layers were separated
  2. washthe organic layer was washed with brine solution (2×50 mL)
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. customRemoval of the solvents and purification of the crude mixture by column chromatography on silica gel (ISCO System)

Sources & evidence

ORD record
ord-adca9a47fc6c4266b3350956482c9912
Source dataset
uspto-grants-2016_04
Patent number
US09321763B2

Reaction notes

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