Dimethyl Sulfoxide → Ethyl 4-(N-BOC-4-piperidyl)trans-crotonate

HRID 636676Notes

Reaction equation

HRID 636676 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([N:18]1[CH2:23][CH2:22][CH:21]([CH2:24][CH2:25]O)[CH2:20][CH2:19]1)([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12].[C:27]([CH:32]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:29][CH2:30][CH3:31])=[O:28]>C(Cl)Cl>[C:11]([N:18]1[CH2:19][CH2:20][CH:21]([CH2:24]/[CH:25]=[CH:32]/[C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH2:22][CH2:23]1)([O:13][C:14]([CH3:15])([CH3:16])[CH3:17])=[O:12]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 8541401-(tert-Butoxycarbonyl)-4-(2-hydroxyethyl)piperidine

Product 1

HCID 10017534Ethyl 4-(N-BOC-4-piperidyl)trans-crotonateYield 54.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of oxalyl chloride (0.43 mL, 5.0 mmol) in CH2Cl2 (30 mL) at −78° C. is added DMSO (0.52 mL, 7.0 mmol) dropwise. After gas evolution subsided (5 min), the alcohol of Example 4 (0.8 g, 3.5 mmol) in CH2Cl2 (20 mL) is added in a stream. After 20 min, (carbethoxymethylene) triphenyl-phosphorane (1.4 g, 4.0 mmol) is added. After 2 h, the reaction mixture is diluted with petroleum ether, washed with water, 5% KHSO4 and sat. NaCl, dried over MgSO4, and concentrated. Flash column chromatography (15% EtOAc in hexane) gave the title compound (0.57 g, 38%) as a colorless oil.

Workup

  1. custom(5 min)
  2. waitAfter 2 h
  3. washwashed with water, 5% KHSO4 and sat. NaCl
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-a8192986a68049668be8ddcbe266aac1
Source dataset
uspto-grants-2001_02
Patent number
US06194435B1

Reaction notes

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