Methanol → tert-Butyl 4-ethynylpiperidine-1-carboxylate

HRID 1676315Notes

Reaction equation

HRID 1676315 reaction equation
[CH:1]([CH:3]1[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1)=O.[C:16]([O-])([O-])=O.[K+].[K+].CO.O=C(C)C(P(=O)(OC)OC)=[N+]=[N-]>CCOCC>[C:1]([CH:3]1[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1)#[CH:16]

Participants

6

Reactant 4

HCID 887MethanolHCID 11430Potassium CarbonateHCID 1514430tert-Butyl 4-formylpiperidine-1-carboxylateHCID 136023029(1E)-1-diazo-1-dimethoxyphosphorylpropan-2-one

Product 1

HCID 15550481tert-Butyl 4-ethynylpiperidine-1-carboxylate

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a stirred suspension of tert-butyl 4-formylpiperidine-1-carboxylate (0.427 g, 2.00 mmol), K2CO3 (0.553 g, 4.00 mmol), and MeOH (25 mL) was added all at once the Bestman-Ohira reagent, dimethyl 2-oxo-1-diazo-propylphosphonate (0.461 g, 2.40 mmol, see Synthesis 2004, 1, 59-62). Stirring was continued for 20 hours under nitrogen. The reaction was diluted with Et2O (50 mL), washed with a 2:1 mixture of water and aqueous saturated NaHCO3 (20 mL), dried (Na2SO4), filtered, and concentrated in vacuo. Yield: 253 mg (55%). 1H NMR (400 MHz, CDCl3) δ 3.72 (m, 2H), 3.19 (m, 2H), 2.58 (m, 1H), 2.10 (d, J=2 Hz, 1H), 1.77 (m, 2H), 1.61 (m, 2H), 1.46 (s, 9H).

Workup

  1. washwashed with a 2:1 mixture of water and aqueous saturated NaHCO3 (20 mL)
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3422c2b03a5f47bb9d81846bda81be21
Source dataset
uspto-grants-2011_08
Patent number
US08003662B2

Reaction notes

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