HCID 89619215, compound → Tert-butyl 2-(4-methyl-5-pivalamidopyridin-2-yl)acetate

HRID 1502121Notes

Reaction equation

HRID 1502121 reaction equation
Br[C:2]1[N:7]=[CH:6][C:5]([NH:8][C:9](=[O:14])[C:10]([CH3:13])([CH3:12])[CH3:11])=[C:4]([CH3:15])[CH:3]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.[Cl-].[C:85]([O:89][C:90](=[O:93])[CH2:91][Zn+])([CH3:88])([CH3:87])[CH3:86].[NH4+].[Cl-].[Cl-].[Na+].O>O1CCCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:15][C:4]1[C:5]([NH:8][C:9](=[O:14])[C:10]([CH3:13])([CH3:12])[CH3:11])=[CH:6][N:7]=[C:2]([CH2:91][C:90]([O:89][C:85]([CH3:88])([CH3:87])[CH3:86])=[O:93])[CH:3]=1

Participants

7

Reactant 4

HCID 89619215HCID 89619215, compoundHCID 118107187HCID 118107187, compoundHCID 131728592Ammonium chloride brineHCID 178451183HCID 178451183, compound

Product 1

HCID 89619062Tert-butyl 2-(4-methyl-5-pivalamidopyridin-2-yl)acetate

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

N-(6-bromo-4-methylpyridin-3-yl) pivalamide (0.644 g, 2.375 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl X-Phos (0.068 g, 0.143 mmol) and tris(dibenzylideneacetone)dipalladium(0) (0.065 g, 0.071 mmol) were dissolved in tetrahydrofuran (30 ml) then added 2-(tert-butoxy)-2-oxoethylzinc chloride (14.25 ml, 7.13 mmol). The mixture was placed into three tubes and microwaved at 100° C. for 1.5 hr. The reactions were poured into NH4Cl/brine solution and extracted with ETOAc (2×), dried over Na2SO4, filtered and concentrated. The residue was chromatographed through an 80 g ISCO Redi-sep column and eluted with ethyl acetate/hexane 1:2 to yield tert-butyl 2-(4-methyl-5-pivalamidopyridin-2-yl)acetate: LC-MS: M+1=307, 251 (M-56)

Workup

  1. custommicrowaved at 100° C. for 1.5 hr
  2. extractionextracted with ETOAc (2×)
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was chromatographed through an 80 g ISCO Redi-sep column
  7. washeluted with ethyl acetate/hexane 1:2

Sources & evidence

ORD record
ord-9b9fe2c498d945919606994d5a4972a3
Source dataset
uspto-grants-2015_12
Patent number
US09206199B2

Reaction notes

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