Pivalaldehyde → HCID 118021359, compound

HRID 1484503Notes

Reaction equation

HRID 1484503 reaction equation
C([Si]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([O:16][CH2:17][O:18][CH3:19])[CH:11]=1)(C)C)(C)(C)C.C([Li])CCC.[CH3:25][C:26]([CH3:30])([CH3:29])[CH:27]=[O:28].[F-].C([N+](CCCC)(CCCC)CCCC)CCC>CCCCCC.C1COCC1.[Cl-].[NH4+]>[OH:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([O:16][CH2:17][O:18][CH3:19])[C:11]=1[CH:27]([OH:28])[C:26]([CH3:30])([CH3:29])[CH3:25]

Participants

8

Reactant 4

HCID 12417PivalaldehydeHCID 2724141Tetrabutylammonium FluorideHCID 67958400HCID 67958400, compound2×HCID 178418339Butyllithium

Product 1

HCID 118021359HCID 118021359, compoundYield 66.6%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×HCID 25517Ammonium ChlorideSolvent

Procedure

To a solution of tert-butyl-[[3-(methoxymethoxy)phenyl]methoxy]-dimethyl-silane (WO2012/076877 Intermediate 103, 500 mg, 1.77 mmol) in dry Hexane (5 mL), at room temperature, butyllithium 1.6M solution in Hexane (1.33 ml, 2.12 mmol) was slowly added and the reaction mixture was stirred for 2 hours at the same temperature. 2,2-dimethylpropanal (152.5 mg, 1.77 mmol) was added and the reaction mixture was stirred for further 30 minutes at the same temperature. The reaction was quenched with water (5 ml), diluted with an aqueous saturated solution of ammonium chloride (20 ml), and extracted with ethyl acetate (2×50 ml). The organic layer was dried (Na2SO4), filtered and evaporated. The residue was dissolved in THF (10 mL) and a 1M solution in THF of tetrabutylammonium fluoride (1.77 ml, 1.77 mmol) was added. The reaction mixture was stirred for 30 minutes at room temperature. The reaction was diluted with an aqueous saturated solution of ammonium chloride (20 ml), and extracted with ethyl acetate (2×50 ml). The organic layer was dried (Na2SO4), filtered and evaporated and the residue was purified by flash chromatography (Biotage system) on silica gel using a SNAP 25 g as column and cyclohexane/ethyl acetate from 100:0 to 70:30 as eluent affording the title compound (300 mg) as colorless oil.

Workup

  1. stirringthe reaction mixture was stirred for further 30 minutes at the same temperature
  2. customThe reaction was quenched with water (5 ml)
  3. additiondiluted with an aqueous saturated solution of ammonium chloride (20 ml)
  4. extractionextracted with ethyl acetate (2×50 ml)
  5. dry with materialThe organic layer was dried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated
  8. dissolutionThe residue was dissolved in THF (10 mL)
  9. stirringThe reaction mixture was stirred for 30 minutes at room temperature
  10. extractionextracted with ethyl acetate (2×50 ml)
  11. dry with materialThe organic layer was dried (Na2SO4)
  12. filtrationfiltered
  13. customevaporated
  14. customthe residue was purified by flash chromatography (Biotage system) on silica gel using a SNAP 25 g as column and cyclohexane/ethyl acetate from 100:0 to 70:30 as eluent

Sources & evidence

ORD record
ord-942a0c054cf1465e8afd2cdd9a32d2d8
Source dataset
uspto-grants-2016_08
Patent number
US09422252B2

Reaction notes

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