Methyl 3-methyl-2-butenoate → HCID 59652062, compound

HRID 2042596Notes

Reaction equation

HRID 2042596 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH:15]([O:18][Si](C)(C)C)C#N)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li+].CC([N-][CH:28]([CH3:30])[CH3:29])C.CC(C)=[CH:33][C:34]([O:36][CH3:37])=[O:35].[NH4+].[Cl-].[CH3:41]CCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[CH2:37]([O:36][C:34](=[O:35])[CH2:33][C:28]([CH3:29])([CH3:30])[C:15]([C:12]1[CH:11]=[CH:10][C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:14][CH:13]=1)=[O:18])[CH3:41]

Participants

7

Reactant 5

HCID 13546Methyl 3-methyl-2-butenoateHCID 25517Ammonium ChlorideHCID 2724141Tetrabutylammonium FluorideHCID 2724682Lithium diisopropylamideHCID 15327372HCID 15327372, compound

Product 1

HCID 59652062HCID 59652062, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

(4-Benzyloxy-phenyl)-trimethylsilanyloxy-acetonitrile (3.0 g, 9.63 mmol) in THF (100 mL) under a nitrogen atmosphere was added LDA (7.2 mL of 2 M in THF) at −72° C. After 0.5 h, methyl 3-methylbut-2-enoate (1.23 mL, 10.1 mmol) in 1 THF (15 mL) was added dropwise. The reaction was stirred at 0° C. for 4 h, and then saturated NH4Cl was added. The THF was removed at reduced pressure; Et2O was added (50 mL) and washed with saturated NH4Cl, water, dried (Na2SO4), and concentrated to give an oil. The oil was dissolved in THF (50 mL) and TBAF (10.1 mL of 1 M THF solution) was added at 0° C. dropwise. After stirring 12 h at rt the reaction was concentrated, dissolved in Et2O and washed with water, NaCl solution and dried (MgSO4). The product was purified by silica gel chromatography (10-20% EtOAc/hexanes) to give 1.5 g; Mp 72-73.

Workup

  1. customThe THF was removed at reduced pressure
  2. additionEt2O was added (50 mL)
  3. washwashed with saturated NH4Cl, water
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customto give an oil
  7. stirringAfter stirring 12 h at rt the reaction
  8. concentrationwas concentrated
  9. dissolutiondissolved in Et2O
  10. washwashed with water, NaCl solution
  11. dry with materialdried (MgSO4)
  12. customThe product was purified by silica gel chromatography (10-20% EtOAc/hexanes)
  13. customto give 1.5 g

Sources & evidence

ORD record
ord-d1cba7e25a8345bba89e387c00201272
Source dataset
uspto-grants-2013_11
Patent number
US08586588B2

Reaction notes

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