Hexane → 2-Acetyl-6-(((tert-butyldimethylsilyl)oxy)methyl)pyridine

HRID 2218950

Reaction equation

HRID 2218950 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])[N:3]=1.CCCCCC.[Li]CCCC.[CH3:28][C:29](N(C)C)=[O:30]>CCOCC.C1COCC1>[C:29]([C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])[N:3]=1)(=[O:30])[CH3:28]

Participants

7

Reactant 4

HCID 8058HexaneHCID 31374DimethylacetamideHCID 11483477Pyridine, 2-bromo-6-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-HCID 178418339Butyllithium

Product 1

HCID 597709522-Acetyl-6-(((tert-butyldimethylsilyl)oxy)methyl)pyridine

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 2-Bromo-6-(((tert-butyldimethylsilyl)oxy)methyl)pyridine (1.59 g, 5.26 mmol) in a mixture of ether, hexane and THF (2:1:1, 105 mL) was added n-BuLi (3.29 mL, 5.26 mmol, 1.6 M in hexane solution) dropwise at −78° C. during 5-10 min. To the resulting dark brown solution was dropped anhydrous DMA (0.74 mL, 7.89 mmol) at the same temperature. The reaction mixture was stirred for 30 min and then quenched with water (8 mL) and extracted with EtOAc. The organic layer was washed with water and brine and dried over MgSO4. After purification by column chromatography on silica gel (hexane/EtOAc 98:2) 0.78 g (56%) of the title compound as an oil were obtained. 1H NMR (CDCl3) δ 7.95 (d, 1H, J=7.5 Hz, H-3), 7.88 (t, 1H, J=7.6 Hz, H-4), 7.73 (t, 1H, J=7.6 Hz, H-5), 4.93 (s, 2H, CH2), 2.75 (s, 3H, CH3), 1.03 (s, 9H, (CH3)3C), 0.20 (s, 6H, (Me)2Si); 13C NMR (CDCl3) δ 200.8 (CO), 161.4 (C-6), 153.0 (C-2), 139.4 (C-4), 124.0 (C-5), 118.0 (C-3), 66.4 (CH2), 26.3 ((CH3)3C), 18.8 ((CH3)3C), -4.96 ((Me)2Si).

Workup

  1. customquenched with water (8 mL)
  2. extractionextracted with EtOAc
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried over MgSO4
  5. customAfter purification by column chromatography on silica gel (hexane/EtOAc 98:2) 0.78 g (56%) of the title compound as an oil
  6. customwere obtained

Sources & evidence

ORD record
ord-4af98cd9957c417b8ae94fdec38ce77e
Source dataset
uspto-grants-2008_08
Patent number
US07414036B2

Linked notes

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