Phosphine, triphenyl-, hydrobromide → 3-Methylene-piperidine-1-carboxylic acid tert-butyl ester

HRID 1162085Notes

Reaction equation

HRID 1162085 reaction equation
O=[C:2]1[CH2:7][CH2:6][CH2:5][N:4]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:3]1.[Br-].[C:16]1([PH+](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Li]CCCC>>[CH2:16]=[C:2]1[CH2:7][CH2:6][CH2:5][N:4]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:3]1

Participants

4

Reactant 3

HCID 517696Phosphine, triphenyl-, hydrobromideHCID 2756825Tert-butyl 3-oxopiperidine-1-carboxylateHCID 178418339Butyllithium

Product 1

HCID 112525943-Methylene-piperidine-1-carboxylic acid tert-butyl ester

Procedure

The title compound was prepared according to the procedure of Intermediate 71 starting from tert-butyl 3-oxopiperidine-1-carboxylate (1 g, 5.0 mmol), triphenylphosphonium bromide (2.69 g, 7.5 mmol) and n-BuLi (1.8 M; 4.2 mL, 7.5 mmol). Yield: 0.28 g (28%) after purification by flash chromatography with 10% isohexane in DCM as eluent. HPLC purity 95%, RT=2.43 min (System A; 10-97% MeCN over 3 min); 90%, RT=2.38 min (System B; 10-97% MeCN over 3 min). 1H NMR (400 MHz, CDCl3) δ ppm 1.41-1.48 (m, 9H) 1.56-1.65 (m, 2H) 2.20-2.30 (m, 2H) 3.38-3.47 (m, 2H) 3.86 (s, 2H) 4.74 (s, 1H) 4.80 (s, 1H). MS (ESI+) for C11H19NO2 m/z 142 (M-C4H8)+. *Previously reported in Tetrahedron 2002, 58, 7165-7175.

Workup

  1. customYield: 0.28 g (28%) after purification by flash chromatography with 10% isohexane in DCM as eluent
  2. custom90%, RT=2.38 min (System B; 10-97% MeCN over 3 min)

Sources & evidence

ORD record
ord-086b2243f65a4f0788de1816d923f649
Source dataset
uspto-grants-2010_10
Patent number
US07820675B2

Reaction notes

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