Cesium carbonate → HCID 68414099, compound

HRID 1880008Notes

Reaction equation

HRID 1880008 reaction equation
Br[C:2]1[C:7]([CH2:8][NH:9][CH3:10])=[CH:6][C:5]([Br:11])=[CH:4][N:3]=1.N1CCC1=O.C([O-])([O-])=O.[Cs+].[Cs+].C[C:24]1([CH3:64])[C:50]2[C:45](=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)[O:44]C2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Br:11][C:5]1[CH:6]=[C:7]([CH2:8][NH:9][CH3:10])[C:2]([CH:64]2[CH2:24][CH2:50][C:45]2=[O:44])=[N:3][CH:4]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 1367212-AzetidinoneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 59332890HCID 59332890, compound

Product 1

HCID 68414099HCID 68414099, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

A solution of (2,5-dibromopyridin-3-yl)-N-methylmethanamine (95 mg, 0.47 mmol), azetidinone (34 mg, 0.47 mmol), Cs2CO3 (308 mg, 0.94 mmol) in 5 mL of toluene was degassed with bubbling argon for 30 min followed by the addition of Pd2(dba)3 (6 mg, 0.01 mmol) and Xantphos (12 mg, 0.02 mmol). The resulting yellow solution was then stirred at 90° C. 18 h. The dark coloured solution was removed from the heat and poured over a pad of celite washing with 50 mL of ethyl acetate. The filtrate was diluted with 50 mL of water, the organic layer was washed with brine, dried over MgSO4, and concentrated in vacuo. The crude product was purified using flash chromatography on silica gel using 95% dichloromethane:methanol to obtain the product as a orange sticky solid. Yield 66 mg (73%); 1H NMR (400 MHz, DMSO-d6) δ 8.09 (d, J=4.8 Hz, 1H), 7.28 (d, J=7.2 Hz, 1H), 6.78 (m, 1H), 4.92 (bs, 1H), 4.51 (s, 2H), 3.58 (q, J=6.0 Hz, 2H), 3.04 (t, J=6.8 Hz, 2H), 2.84 (s, 3H); ESI MS m/z 192 [C10H13N3O+H]+

Workup

  1. custom18 h
  2. customThe dark coloured solution was removed from the
  3. temperatureheat
  4. additionpoured over a pad of celite
  5. washwashing with 50 mL of ethyl acetate
  6. additionThe filtrate was diluted with 50 mL of water
  7. washthe organic layer was washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated in vacuo
  10. customThe crude product was purified

Sources & evidence

ORD record
ord-213f54ac97f64e5c9989214edc7138f9
Source dataset
uspto-grants-2012_11
Patent number
US08318720B2

Reaction notes

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