Acetic acid, 2-(triphenylphosphoranylidene)-, methyl ester → HCID 53718989, compound

HRID 1976613Notes

Reaction equation

HRID 1976613 reaction equation
CO[C:3](=O)[C@@H:4]1[CH2:9][CH2:8][CH2:7][CH2:6][N:5]1[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].[H-].C([Al+]CC(C)C)C(C)C.C1(P(=[CH:47][C:48]([O:50][CH3:51])=[O:49])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[C:13]([O:12][C:10]([N:5]1[CH2:6][CH2:7][CH2:8][CH2:9][C@H:4]1[CH:3]=[CH:47][C:48]([O:50][CH3:51])=[O:49])=[O:11])([CH3:14])([CH3:15])[CH3:16]

Participants

5

Reactant 3

HCID 17453Acetic acid, 2-(triphenylphosphoranylidene)-, methyl esterHCID 108241391-tert-Butyl 2-methyl (2S)-piperidine-1,2-dicarboxylateHCID 21225700Diisobutylaluminumhydride2×

Product 1

HCID 53718989HCID 53718989, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A stirred solution of (S)-N-(t-butoxycarbonyl)-pipecolinic acid methyl ester (2.04 g, 8.39 mmol) in methylene chloride (75 mL) at −78° C. under nitrogen was treated with diisobutylaluminum hydride (1.0 M in toluene, 14.2mL, 14.2 mmol). After 1.25 h a second aliquot of diisobutylaluminum hydride (2.00 mL, 2.00 mmol) was added. The mixture was stirred for an additional 30 min. and then quenched by the addition of a 20% aqueous Rochelle's salt solution (100 mL) followed by vigorous stirring for 1 h. The aqueous layer was extracted with methylene chloride and the combined organic extracts were dried over magnesium sulfate, filtered, and concentrated. The crude aldehyde was dissolved in methylene chloride (100 mL) and treated with methyl (triphenylphosphoranylidene)acetate (4.00 g, 12.0 mmol). After 15 hours (h) the reaction mixture was concentrated and purified by flash chromatography to give the desired product (1.46 g, 65%).

Workup

  1. customquenched by the addition of a 20% aqueous Rochelle's salt solution (100 mL)
  2. stirringby vigorous stirring for 1 h
  3. extractionThe aqueous layer was extracted with methylene chloride
  4. dry with materialthe combined organic extracts were dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutionThe crude aldehyde was dissolved in methylene chloride (100 mL)
  8. concentrationAfter 15 hours (h) the reaction mixture was concentrated
  9. custompurified by flash chromatography

Sources & evidence

ORD record
ord-438f68bbb1c847b1964fca31bd2085f9
Source dataset
uspto-grants-2001_05
Patent number
US06228872B1

Reaction notes

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