Water → (E)-tert-butyl 4-methyl-4-((5-oxohex-3-en-1-yl)oxy)piperidine-1-carboxylate

HRID 921141Notes

Reaction equation

HRID 921141 reaction equation
[CH3:1][C:2]1([O:15][CH2:16][CH2:17][CH:18]=O)[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.C1(P(C2C=CC=CC=2)(C2C=CC=CC=2)=[CH:27][C:28](=[O:30])[CH3:29])C=CC=CC=1.O>C(Cl)Cl>[CH3:1][C:2]1([O:15][CH2:16][CH2:17]/[CH:18]=[CH:27]/[C:28](=[O:30])[CH3:29])[CH2:3][CH2:4][N:5]([C:8]([O:10][C:11]([CH3:12])([CH3:13])[CH3:14])=[O:9])[CH2:6][CH2:7]1

Participants

5

Reactant 3

HCID 962WaterHCID 150381-(Triphenylphosphoranylidene)acetoneHCID 118307084Tert-butyl 4-methyl-4-(3-oxopropoxy)piperidine-1-carboxylate

Product 1

HCID 118307125(E)-tert-butyl 4-methyl-4-((5-oxohex-3-en-1-yl)oxy)piperidine-1-carboxylateYield 80.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of tert-butyl 4-methyl-4-(3-oxopropoxy)piperidine-1-carboxylate (5.7 g, 21.01 mmol) in CH2Cl2 (150 mL) was added 1-(triphenylphosphoranylidene)propan-2-one (8.69 g, 27.3 mmol) and the resulting mixture was stirred at room temp for 16 h. Water was then added and the mixture was extracted with dichloromethane, dried (Na2SO4), filtered and concentrated. The residue was then purified by Biotage (5-40% EtOAc/hexane) to afford (E)-tert-butyl 4-methyl-4-((5-oxohex-3-en-1-yl)oxy)piperidine-1-carboxylate (5.25 g, 16.86 mmol, 80% yield) as colorless oil. 1H NMR (500 MHz, CDCl3) δ 6.85 (dt, J=16.1, 6.9 Hz, 1H), 6.15 (dt, J=16.0, 1.4 Hz, 1H), 3.79-3.66 (m, 2H), 3.47 (t, J=6.4 Hz, 2H), 3.12 (t, J=11.6 Hz, 2H), 2.49 (qd, J=6.5, 1.5 Hz, 2H), 2.29-2.26 (m, 3H), 1.73 (d, J=13.2 Hz, 2H), 1.47 (s, 9H), 1.46-1.39 (m, 2H), 1.18 (s, 3H). LCMS (M+Na)=334.3.

Workup

  1. extractionthe mixture was extracted with dichloromethane
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was then purified by Biotage (5-40% EtOAc/hexane)

Sources & evidence

ORD record
ord-6d4bb0a4c01540f99599fc8575ddac0a
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Reaction notes

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