tert-Butyl (6-methylpyridin-2-yl)carbamate → HCID 59858004, compound

HRID 2378341Notes

Reaction equation

HRID 2378341 reaction equation
[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH3:14])[N:9]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:16][C:17]([CH3:19])=O.[C:20](=[O:22])=O.[Li][CH2:24][CH2:25][CH2:26][CH3:27]>C1COCC1>[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14][CH:13]2[CH:20]([OH:22])[CH2:6][N:7]([CH2:16][C:17]3[CH:19]=[CH:27][CH:26]=[CH:25][CH:24]=3)[CH2:8]2)[N:9]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 11367776tert-Butyl (6-methylpyridin-2-yl)carbamateHCID 18522661Acetone cardiceHCID 178418339Butyllithium

Product 1

HCID 59858004HCID 59858004, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of (6-methyl-pyridin-2-yl)-carbamic acid tert-butyl ester I-1 (0.00625 mol) in 10 mL THF was cooled in a −78° C. bath (acetone/dry ice). n-BuLi (1.6 M in hexanes, 0.0125 mol) was added during 15 min. under N2. The color of solution was changed from colorless to orange. Then the cooling bath was removed. After 45 min stirring at room temperature, the color solution was changed into dark red. The solution was then returned to the −78° C. bath. 3-Benzyl-6-oxa-3-aza-bicyclo[3.1.0]hexane I-2 (0.005 mol) in 10 mL THF was added during 1 h. After 2 h, the cooling bath was removed. The solution was stirred for 2 h more at room temperature. The reaction was quenched by the addition of ice-cold water (50 ml). The mixture was extracted with CH2Cl2 (30 ml×3). The combined organic layers were washed with brine and dried over anhydrous MgSO4. The solvent was removed in vacuo and the residue was purified by column chromatography (silica gel, CH2Cl2 MeOH, 9:1) (90%).

Workup

  1. customThen the cooling bath was removed
  2. customwas then returned to the −78° C. bath
  3. addition(0.005 mol) in 10 mL THF was added during 1 h
  4. waitAfter 2 h
  5. customthe cooling bath was removed
  6. stirringThe solution was stirred for 2 h more at room temperature
  7. customThe reaction was quenched by the addition of ice-cold water (50 ml)
  8. extractionThe mixture was extracted with CH2Cl2 (30 ml×3)
  9. washThe combined organic layers were washed with brine
  10. dry with materialdried over anhydrous MgSO4
  11. customThe solvent was removed in vacuo
  12. customthe residue was purified by column chromatography (silica gel, CH2Cl2 MeOH, 9:1) (90%)

Sources & evidence

ORD record
ord-fcb8278f59664d83a70a25e052714d26
Source dataset
uspto-grants-2008_12
Patent number
US07470790B2

Reaction notes

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