tert-Butyl carbamate → HCID 86680796, compound

HRID 2402371Notes

Reaction equation

HRID 2402371 reaction equation
[C:1](=[O:8])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])[NH2:2].[Br:9][C:10]1[CH:15]=[C:14]([CH3:16])[CH:13]=[C:12](Br)[N:11]=1.CC(C)([O-])C.[Na+]>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].C(P(C(C)(C)C)[C-]1C=CC=C1)(C)(C)C.[C-]1(P(C(C)(C)C)C(C)(C)C)C=CC=C1.[Fe+2]>[Br:9][C:10]1[N:11]=[C:12]([NH:2][C:1](=[O:8])[O:3][C:4]([CH3:7])([CH3:6])[CH3:5])[CH:13]=[C:14]([CH3:16])[CH:15]=1

Participants

6

Reactant 3

HCID 77922tert-Butyl carbamateHCID 112881742,6-Dibromo-4-methylpyridineHCID 23676156Sodium t-butoxide

Product 1

HCID 86680796HCID 86680796, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 12976736Bis(ditert-butyl(cyclopenta-2,4-dien-1-yl)phosphane);iron(2+)Catalyst

Conditions

Temperature
70 °C

Procedure

Into a flask were added tert-butyl carbamate (5.6 g, 47.8 mmol) and 2,6-dibromo-4-methyl-pyridine (12 g, 47.8 mmol) followed by degassed 2-MeTHF (120 mL). Solid sodium tert-butoxide (4.6 g, 47.8 mmol) was then added followed by tris(dibenzylideneacetone)dipalladium(0) (1.1 g, 1.2 mmol) and 1,1′-bis(di-tert-butylphosphino)ferrocene (1.1 g, 2.4 mmol), and the solution evacuated and refilled with nitrogen 3 times. The solution was heated to 70° C. for 4 h and then cooled to rt. The mixture was treated with water (20 mL) and EtOAc (100 mL) and filtered through Celite®. The organic solution was washed with brine (100 mL) and then concentrated under reduced pressure. The resulting residue was purified via silica gel chromatography to afford tert-butyl (6-bromo-4-methylpyridin-2-yl)carbamate (11.2 g, 82%) as a white solid. MS ESI calcd for C11H15BrN2O2 [M+H]+ 287, found 287. 1H NMR (600 MHz, CDCl3) δ 7.70 (s, 1H), 7.13 (s, 1H), 6.95 (s, 1H), 2.29 (s, 3H), 1.49 (s, 9H) ppm.

Workup

  1. customby degassed 2-MeTHF (120 mL)
  2. customthe solution evacuated
  3. additionrefilled with nitrogen 3 times
  4. temperaturecooled to rt
  5. additionThe mixture was treated with water (20 mL) and EtOAc (100 mL)
  6. filtrationfiltered through Celite®
  7. washThe organic solution was washed with brine (100 mL)
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting residue was purified via silica gel chromatography

Sources & evidence

ORD record
ord-96b3a9404ad449dc822afdc1f8771d37
Source dataset
uspto-grants-2014_08
Patent number
US08796310B2

Reaction notes

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