Potassium Carbonate → tert-Butyl 3-ethynylpiperidine-1-carboxylate

HRID 535861

Reaction equation

HRID 535861 reaction equation
[C:1]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([CH:14]=O)[CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH3:16]OP(C=[N+]=[N-])(=O)OC.C([O-])([O-])=O.[K+].[K+]>CO>[C:1]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([C:14]#[CH:16])[CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 5115033Dimethyl (diazomethyl)phosphonateHCID 99644481-Boc-piperidine-3-carboxaldehyde

Product 1

HCID 21963855tert-Butyl 3-ethynylpiperidine-1-carboxylateYield 100.4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of 1-BOC-3-formylpiperidine (1.46 g, 6.85 mmol) and (diazomethyl) phosphonic acid dimethyl ester (1.79 g, 11.94 mmol) in 50 mL methanol was stirred at ice-bath for 10 min, K2CO3 (1.96 g, 14.2 mmol) was added to the above mixture and stirred at ice-bath for 2 hrs, then stirred at rt overnight. The mixture was evaporated in vacuo, to the residue was added EtOAc and water, the organic layer was separated and water layer was extracted with EtOAc (100 mL×3). The combined organic layers were washed with water and brine successively, dried with Na2SO4, filtered, and the filtrate was evaporated in vacuo to give 1.44 g product as colorless oil (100.0%). 1H NMR (300 MHz, CDCl3) δ: 3.90 (1H, brs), 3.70-3.75 (1H, m), 2.95-3.02 (2H, m), 2.40-2.47 (1H, m), 2.05 (1H, d, J=2.1 Hz), 1.94-1.99 (1H, m), 1.69-1.73 (1H, m), 1.50-1.63 (2H, m), 1.46 (9H, s).

Workup

  1. stirringstirred at rt overnight
  2. customThe mixture was evaporated in vacuo, to the residue
  3. additionwas added EtOAc and water
  4. customthe organic layer was separated
  5. extractionwater layer was extracted with EtOAc (100 mL×3)
  6. washThe combined organic layers were washed with water and brine successively
  7. dry with materialdried with Na2SO4
  8. filtrationfiltered
  9. customthe filtrate was evaporated in vacuo

Sources & evidence

ORD record
ord-fee5f01557c74cd9a77029b6804140ff
Source dataset
uspto-grants-2014_10
Patent number
US08859553B2

Linked notes

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