Diisopropylamine → HCID 131730229, compound

HRID 388749Notes

Reaction equation

HRID 388749 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.C[Si]([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])(C)C.[Si:23]([O:30][C@H:31]1[C:36](=[CH2:37])[C@H:35]([CH2:38][O:39][Si:40]([C:43]([CH3:46])([CH3:45])[CH3:44])([CH3:42])[CH3:41])[CH2:34][C:33](=O)[CH2:32]1)([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24]>O1CCCC1>[Si:23]([O:30][C@H:31]1[C:36](=[CH2:37])[C@H:35]([CH2:38][O:39][Si:40]([C:43]([CH3:46])([CH3:45])[CH3:44])([CH3:41])[CH3:42])[CH2:34]/[C:33](=[CH:17]\[C:18]([O:20][CH2:21][CH3:22])=[O:19])/[CH2:32]1)([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24]

Participants

6

Reactant 4

HCID 7912DiisopropylamineHCID 77687Ethyl trimethylsilylacetateHCID 57696870HCID 57696870, compoundHCID 178418339Butyllithium

Product 1

HCID 131730229HCID 131730229, compoundYield 59.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

n-Butyllithium (2.5 M in hexanes, 1.6 mL, 4 mmol) was added to a solution of diisopropylamine (0.56 mL, 4 mmol) in 5 mL of tetrahydrofuran at −78° C. After 30 minutes, ethyl trimethylsilylacetate (0.73 mL, 4 mmol) was added. After stirring 30 minutes, a solution of the compound of Example 16J (787 mg, 2 mmol) in 8 mL of tetrahydrofuran was added, followed by a rinse of 2 mL of tetrahydrofuran. After 2 hours, the reaction was quenched by the addition of 10 mL of saturated aqueous NH4Cl. After warming to ambient temperature, the mixture was poured into 100 mL of 20% NaCl, then extracted twice with 100 mL of tert-butyl methyl ether. The combined tert-butyl methyl ether extracts were dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (300 mL of SiO2, elution with a gradient of 1:1 dichloromethane:hexanes to dichloromethane) to afford 538 mg (58% yield) of a ˜4:1 mixture of isomers favoring the title compound (538 mg, 58%).

Workup

  1. washa rinse of 2 mL of tetrahydrofuran
  2. waitAfter 2 hours
  3. customthe reaction was quenched by the addition of 10 mL of saturated aqueous NH4Cl
  4. additionthe mixture was poured into 100 mL of 20% NaCl
  5. extractionextracted twice with 100 mL of tert-butyl methyl ether
  6. dry with materialThe combined tert-butyl methyl ether extracts were dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by silica gel chromatography (
  10. wash300 mL of SiO2, elution with a gradient of 1:1 dichloromethane
  11. customhexanes to dichloromethane) to afford
  12. addition538 mg (58% yield) of a ˜4:1 mixture of isomers

Sources & evidence

ORD record
ord-97ce6900c676451095eba821c6f856b4
Source dataset
uspto-grants-2013_02
Patent number
US08377913B2

Reaction notes

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