Ethyl isobutyrate → Ethyl 2,2-dimethylnon-8-enoate

HRID 1669570Notes

Reaction equation

HRID 1669570 reaction equation
[Li]CCCC.C(N[CH:10]([CH3:12])[CH3:11])(C)C.[CH2:13]([O:15][C:16](=[O:20])C(C)C)[CH3:14].Br[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH:27]=[CH2:28]>C1COCC1.CN(P(N(C)C)(N(C)C)=O)C>[CH2:13]([O:15][C:16](=[O:20])[C:10]([CH3:11])([CH3:12])[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH:23]=[CH2:22])[CH3:14]

Participants

7

Reactant 4

HCID 7342Ethyl isobutyrateHCID 7912DiisopropylamineHCID 5244507-Bromo-1-hepteneHCID 178418339Butyllithium

Product 1

HCID 59497201Ethyl 2,2-dimethylnon-8-enoateYield 44%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 12679HexamethylphosphoramideSolvent

Procedure

A solution of n-BuLi 2.5 M in hexanes (3.79 mL, 9.48 mmol) was added at −78° C. under nitrogen to a solution of diisopropylamine (1.33 mL, 9.46 mmol) in dry THF (10 mL). After 15 min, a solution of ethylisobutyrate (1.0 g, 8.61 mmol) in dry THF (5.0 mL) was slowly added. After 30 min at −78° C., a solution of 7-bromohept-1-ene (1.68 g, 9.47 mmol) in HMPA (2.0 mL) was added drop wise and the reaction mixture was allowed to warm up to room temperature. After 16 h, the reaction mixture was quenched with diluted HCl, extracted with AcOEt, washed with brine, dried (MgSO4), filtered and concentrated. Purification by flash chromatography (DCM/heptane, 2:8) afforded 800 mg (44%) of the title product (51) as a colorless oil. TLC (DCM/hexanes 1/1): Rf=0.7.

Workup

  1. waitAfter 30 min at −78° C.
  2. waitAfter 16 h
  3. customthe reaction mixture was quenched with diluted HCl
  4. extractionextracted with AcOEt
  5. washwashed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by flash chromatography (DCM/heptane, 2:8)

Sources & evidence

ORD record
ord-50056da0215546eabf46867c8dd22ecb
Source dataset
uspto-grants-2011_08
Patent number
US07989471B2

Reaction notes

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