Tert-butyl 2-(acetoxymethyl)-4-hydroxypiperidine-1-carboxylate → Tert-butyl 2-(acetoxymethyl)-4-oxopiperidine-1-carboxylate

HRID 2179413Notes

Reaction equation

HRID 2179413 reaction equation
[C:1]([O:4][CH2:5][CH:6]1[CH2:11][CH:10]([OH:12])[CH2:9][CH2:8][N:7]1[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])(=[O:3])[CH3:2].[Cr](Cl)([O-])(=O)=O.[NH+]1C=CC=CC=1>ClCCl>[C:1]([O:4][CH2:5][CH:6]1[CH2:11][C:10](=[O:12])[CH2:9][CH2:8][N:7]1[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 68109163Tert-butyl 2-(acetoxymethyl)-4-hydroxypiperidine-1-carboxylateHCID 178418287HCID 178418287, compound

Product 1

HCID 68109076Tert-butyl 2-(acetoxymethyl)-4-oxopiperidine-1-carboxylateYield 43%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of the product of step H (506 mg, 1.9 mmol) in dichloromethane (15 mL) at 0° C. was added pyridinium chlorochromate (4.0 g, 19 mmol). The reaction was allowed to warm to ambient temperature and stirred for a further 2 h. The reaction mixture was filtered through celite and the filtrate was concentrated in vacuo to afford the crude product which was purified by flash column chromatography (SiO2, 19:1 to 4:1, hexanes/ethyl acetate) to afford tert-butyl 2-(acetoxymethyl)-4-oxopiperidine-1-carboxylate (220 mg, 43%) as a colorless oil: 1H NMR (CDCl3, 400 MHz) δ 4.57 (br s, 1H), 4.03-3.99 (m, 2H), 3.91-3.87 (m, 1H), 3.28-3.21 (s, 1H), 2.52-2.46 (m, 1H), 2.35-2.31 (m, 1H), 2.26-2.18 (m, 2H), 1.83 (s, 3H), 1.50 (s, 9H).

Workup

  1. filtrationThe reaction mixture was filtered through celite
  2. concentrationthe filtrate was concentrated in vacuo
  3. customto afford the crude product which
  4. customwas purified by flash column chromatography (SiO2, 19:1 to 4:1, hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-64491a4f871646c4b715dc67ecd05b18
Source dataset
uspto-grants-2015_06
Patent number
US09067949B2

Reaction notes

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