Cesium fluoride → 8-(2,5-Dimethyl-4-nitrophenyl)-1,4-dioxaspiro[4.5]dec-7-ene

HRID 2093807Notes

Reaction equation

HRID 2093807 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[CH3:12].CC1(C)C(C)(C)OB([C:21]2[CH2:30][CH2:29][C:24]3([O:28][CH2:27][CH2:26][O:25]3)[CH2:23][CH:22]=2)O1.[F-].[Cs+]>CC(O)C(O)C.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>[CH3:12][C:3]1[CH:4]=[C:5]([N+:9]([O-:11])=[O:10])[C:6]([CH3:8])=[CH:7][C:2]=1[C:21]1[CH2:30][CH2:29][C:24]2([O:28][CH2:27][CH2:26][O:25]2)[CH2:23][CH:22]=1

Participants

7

Reactant 3

HCID 25953Cesium fluorideHCID 8258081-Bromo-2,5-dimethyl-4-nitrobenzeneHCID 36970768-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-dioxaspiro(4.5)dec-7-ene

Product 1

HCID 582571358-(2,5-Dimethyl-4-nitrophenyl)-1,4-dioxaspiro[4.5]dec-7-ene

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 2622,3-ButanediolSolventHCID 962WaterSolvent

Conditions

Temperature
130 °C

Procedure

A mixture of 1-bromo-2,5-dimethyl-4-nitrobenzene (100 mg, 0.43 mmol), 4,4,5,5-tetramethyl-2-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)-1,3,2-dioxaborolane (112 mg, 0.43 mmol), Pd(PPh3)4 (49 mg, 0.043 mmol) and CsF (196 mg, 1.29 mmol) in a mixture of dimethyl ethylene glycol and water (2:1, 1.5 mL) was degassed and heated under N2 at 130° C. in microwave reactor for 15 min. After cooling down to room temperature, the reaction mixture was treated with saturated NH4Cl aqueous solution (5 mL) and extracted with EtOAc (3×4 mL). The combined organic layers were concentrated and purified by flash column chromatography (silica gel, 0%-30% EtOAc in hexanes gradient) to provide 8-(2,5-dimethyl-4-nitrophenyl)-1,4-dioxaspiro[4.5]dec-7-ene as a white solid; ESMS m/z 290.1 (M+H+).

Workup

  1. customwas degassed
  2. temperatureAfter cooling down to room temperature
  3. additionthe reaction mixture was treated with saturated NH4Cl aqueous solution (5 mL)
  4. extractionextracted with EtOAc (3×4 mL)
  5. concentrationThe combined organic layers were concentrated
  6. custompurified by flash column chromatography (silica gel, 0%-30% EtOAc in hexanes gradient)

Sources & evidence

ORD record
ord-a437c0cb1b8947fcac7b3092b2061388
Source dataset
uspto-grants-2013_05
Patent number
US08445505B2

Reaction notes

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