Methyl acetoacetate → E-methyl-5-hydroxy-3-oxo-7-tributylstannyl-6-heptenoate

HRID 1587017Notes

Reaction equation

HRID 1587017 reaction equation
[H-].[Na+].[C:3]([O:9][CH3:10])(=[O:8])[CH2:4][C:5]([CH3:7])=[O:6].C([Li])CCC.[CH2:16]([Sn:20]([CH2:29][CH2:30][CH2:31][CH3:32])([CH2:25][CH2:26][CH2:27][CH3:28])/[CH:21]=[CH:22]/[CH:23]=[O:24])[CH2:17][CH2:18][CH3:19]>O1CCCC1.CCCCCC>[CH3:10][O:9][C:3](=[O:8])[CH2:4][C:5](=[O:6])[CH2:7][CH:23]([OH:24])/[CH:22]=[CH:21]/[Sn:20]([CH2:16][CH2:17][CH2:18][CH3:19])([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:25][CH2:26][CH2:27][CH3:28]

Participants

7

Reactant 4

HCID 7757Methyl acetoacetateHCID 24758Sodium hydrideHCID 109915673-(Tributylstannyl)prop-2-enalHCID 178418339Butyllithium

Product 1

HCID 19759789E-methyl-5-hydroxy-3-oxo-7-tributylstannyl-6-heptenoate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of sodium hydride (1.28 g) in tetrahydrofuran (70 ml) is cooled to 0° C. and methyl acetoacetate (3.2 ml) added over about 1 minute. The mixture is stirred for about 15 minutes at 0° C., 2.5M n-butyllithium in hexane (12.3 ml) added, stirred for about 20 minutes, E-3-tributylstannylacrolein (10.0 g) in tetrahydrofuran (25 ml) added over five minutes and stirred for about 15 minutes. The mixture is quenched by slow addition of 1M hydrochloric acid, diluted with ether. The aqueous layer is back-extracted with ether and the combined organic solutions washed with saturated sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude product is purified by flash chromatography in 25% ethyl acetate in hexane to give the desired product.

Workup

  1. stirringstirred for about 20 minutes
  2. stirringstirred for about 15 minutes
  3. customThe mixture is quenched by slow addition of 1M hydrochloric acid
  4. additiondiluted with ether
  5. extractionThe aqueous layer is back-extracted with ether
  6. washthe combined organic solutions washed with saturated sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude product is purified by flash chromatography in 25% ethyl acetate in hexane

Sources & evidence

ORD record
ord-7f72b4dc01b441adafae659ac0bacce6
Source dataset
uspto-grants-1993_06
Patent number
US05216015

Reaction notes

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