Cesium carbonate → (E)-2-(3,3-diethoxyprop-1-enyl)-1-fluoro-3-nitrobenzene

HRID 1621836Notes

Reaction equation

HRID 1621836 reaction equation
[CH2:1]([O:3][CH:4]([O:16][CH2:17][CH3:18])[CH:5]=[CH:6]B1OC(C)(C)C(C)(C)O1)[CH3:2].Br[C:20]1[C:25]([N+:26]([O-:28])=[O:27])=[CH:24][CH:23]=[CH:22][C:21]=1[F:29].C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.O.[Pd+2].ClC1C=C[C-](P(C2C=CC=CC=2)C2C=CC=CC=2)C=1Cl.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH2:17]([O:16][CH:4]([O:3][CH2:1][CH3:2])/[CH:5]=[CH:6]/[C:20]1[C:25]([N+:26]([O-:28])=[O:27])=[CH:24][CH:23]=[CH:22][C:21]=1[F:29])[CH3:18]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 183734742-Bromo-1-fluoro-3-nitrobenzeneHCID 686781162-(3,3-Diethoxy-1-propen-1-YL)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 68514002(E)-2-(3,3-diethoxyprop-1-enyl)-1-fluoro-3-nitrobenzeneYield 61%

Reagents, catalysts & solvents 3

HCID 178478230HCID 178478230, compoundCatalystHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

A glass microwave reaction vessel was charged with 3,3-diethoxy-1-propenylboronic acid pinacol ester (0.154 mL, 0.600 mmol, Frontier Scientific), 2-bromo-1-fluoro-3-nitrobenzene (110 mg, 0.500 mmol, Aldrich), dichloro 1,1′-bis(diphenylphosphino)ferrocene palladium (II) (40.8 mg, 0.050 mmol, Strem) and cesium carbonate (326 mg, 1.00 mmol, Aldrich) in dioxane (3 mL) and water (0.5 mL). The reaction mixture was stirred and heated in an Emrys Optimizer microwave reactor (Personal Chemistry, Biotage AB, Inc., Upssala, Sweden) at 120° C. for 20 min. The reaction mixture was diluted with water (10 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with saturated NaCl (5 mL) and dried over Na2SO4. The solution was filtered and concentrated in vacuo to give the crude material. The crude product was purified by silica gel chromatography eluting with 10% EtOAc/hexanes to give (E)-2-(3,3-diethoxyprop-1-enyl)-1-fluoro-3-nitrobenzene (82 mg, 0.305 mmol, 60.9% yield). 1H NMR (300 MHz, CDCl3) δ 1.26 (t, J=7.02 Hz, 6H) 3.45-3.81 (m, 4H) 5.09 (d, J=4.09 Hz, 1H) 6.16-6.37 (m, 1H) 6.76 (d, J=17.25 Hz, 1H) 7.29-7.53 (m, 2H) 7.57-7.75 (m, 1H). m/z (ESI, +ve ion) 270 (M+H)+.

Workup

  1. customA glass microwave reaction vessel
  2. extractionextracted with EtOAc (2×20 mL)
  3. washThe combined organic extracts were washed with saturated NaCl (5 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationThe solution was filtered
  6. concentrationconcentrated in vacuo
  7. customto give the crude material
  8. customThe crude product was purified by silica gel chromatography
  9. washeluting with 10% EtOAc/hexanes

Sources & evidence

ORD record
ord-06d8ca6d1ef94606bd16bf6aa4bffd8c
Source dataset
uspto-grants-2014_07
Patent number
US08772480B2

Reaction notes

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