Cesium carbonate → HCID 90135630, compound

HRID 1506789Notes

Reaction equation

HRID 1506789 reaction equation
[CH3:1][C:2]1([CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:11][CH2:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7](B3OC(C)(C)C(C)(C)O3)[CH:8]=2)[C:3]1=[O:21].C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:35]1[CH:40]=[CH:39][C:38]([N+:41]([O-:43])=[O:42])=[CH:37][N:36]=1>O1CCOCC1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][C:2]1([CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:11][CH2:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([C:35]3[CH:40]=[CH:39][C:38]([N+:41]([O-:43])=[O:42])=[CH:37][N:36]=3)[CH:8]=2)[C:3]1=[O:21]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 782402-Bromo-5-nitropyridineHCID 90152014HCID 90152014, compound

Product 1

HCID 90135630HCID 90135630, compoundYield 101%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Procedure

Pd(PPh3)4 (0.248 g, 0.215 mmol) was added to a solution of 3E (1.6 g, 4.3 mmol) in 20 mL of 1,4 dioxane-H2O (3:1) mixture under argon atmosphere, followed by cesium carbonate (4.2 g, 12.89 mmol) and 2-bromo-5-nitropyridine (0.872 g, 4.3 mmol). The mixture was degassed for 5 min. The reaction mixture was refluxed for 3 h, and solvent was removed under reduced pressure. The residue was partitioned between ethyl acetate and water. The separated organic layer was dried over sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by triturating in ethanol to afford the title compound (1.6 g, 69%) as a solid. 1H NMR (400 MHz, CDCl3): δ 9.52 (d, J=2.6 Hz, 1H), 8.57 (dd, J1=2.6 Hz, J2=8.7 Hz, 1H), 8.20 (d, J=8.2 Hz, 1H), 8.02 (s, 1H), 7.97 (dd, J1=3.2 Hz, J2=8.0 Hz, 2H), 4.10 (q, J=7.2 Hz, 2H), 3.19 (m, 1H), 3.06 (dt, J1=17.2 Hz, J2=4.4 Hz, 1H), 2.98 (d, J=15.6 Hz, 1H), 2.56-2.43 (m, 2H), 2.00 (dt, J1=13.5 Hz, J2=4.6 Hz, 1H), 1.31 (s, 3H), 1.22 (t, J=7.2 Hz, 3H). ESI-MS m/z: 369 (M+H)+.

Workup

  1. customThe mixture was degassed for 5 min
  2. temperatureThe reaction mixture was refluxed for 3 h
  3. customsolvent was removed under reduced pressure
  4. customThe residue was partitioned between ethyl acetate and water
  5. dry with materialThe separated organic layer was dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe product was purified
  9. customby triturating in ethanol

Sources & evidence

ORD record
ord-ba414d83351c46cb88e4d378c8284bc1
Source dataset
uspto-grants-2015_12
Patent number
US09221766B2

Reaction notes

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