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

HRID 257737Notes

Reaction equation

HRID 257737 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(N(CC)CC)C.[C:34]([CH:39]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:36][CH2:37][CH3:38])=[O:35]>C(Cl)Cl>[C:11]([N:18]1[CH2:19][CH2:20][CH:21]([CH2:24]/[CH:25]=[CH:39]/[C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH2:22][CH2:23]1)([O:13][C:14]([CH3:15])([CH3:16])[CH3:17])=[O:12]

Participants

7

Reactant 5

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 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 (20 mL) at -78° C. was added DMSO (0.52 ml, 7.0 mmol) dropwise. After gas evolution subsided (~5 minutes) the alcohol 11 (0.8 g, 3.5 mmol) in CH2Cl2 (20 mL) was added in a stream. After 20 minutes triethylamine (1.7 mL, 12 mmol) was added dropwise and then the cooling bath removed. After 20 minutes (carbethoxymethylene) triphenylphosphorane (1.4 g, 4.0 mmol) was added. After 2.0 hours the reaction mixture was diluted with petroleum ether and then washed sequentially with H2O, 5% KHSO4, and brine, dried (MgSO4), and concentrated. Flash chromatography (silica, 15% ethyl acetate/hexanes) gave the ester 12 (0.57 g) as a colorless oil.

Workup

  1. custom(~5 minutes)
  2. additionwas added in a stream
  3. customthe cooling bath removed
  4. washwashed sequentially with H2O, 5% KHSO4, and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-f893610a75244ef295100dedd97561f3
Source dataset
uspto-grants-1993_11
Patent number
US05264420

Reaction notes

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