Diethyl Malonate → HCID 59464079, compound

HRID 1713863Notes

Reaction equation

HRID 1713863 reaction equation
CC1C=CC(S(O[C:12]2[CH:17]=[CH:16][C:15]([CH:18]3[CH2:27][CH2:26][C:21]4([O:25][CH2:24][CH2:23][O:22]4)[CH2:20][CH2:19]3)=[CH:14][CH:13]=2)(=O)=O)=CC=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.C(=O)([O-])[O-].[Cs+].[Cs+].[C:68]([O:76][CH2:77][CH3:78])(=[O:75])[CH2:69][C:70]([O:72][CH2:73][CH3:74])=[O:71]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[O:22]1[C:21]2([CH2:20][CH2:19][CH:18]([C:15]3[CH:14]=[CH:13][C:12]([CH:69]([C:70]([O:72][CH2:73][CH3:74])=[O:71])[C:68]([O:76][CH2:77][CH3:78])=[O:75])=[CH:17][CH:16]=3)[CH2:27][CH2:26]2)[O:25][CH2:24][CH2:23]1

Participants

7

Reactant 4

HCID 7761Diethyl MalonateHCID 10796Cesium carbonateHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 59464315HCID 59464315, compound

Product 1

HCID 59464079HCID 59464079, compoundYield 15%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

4-(1,4-Dioxaspiro[4.5]dec-8-yl)phenyl 4-methylbenzenesulphonate (2.05 g, 5.27 mmol) was stirred with 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) (502 mg, 1.05 mmol) and caesium carbonate (5.15 g, 15.81 mmol) in toluene (40 mL) at room temperature under a nitrogen atmosphere. The reaction mixture was degassed several times then palladium(II) acetate (95 mg, 0.42 mmol) was added, followed by diethyl malonate (0.96 mL, 6.324 mmol). The mixture was heated under reflux for 40 h then was filtered through diatomaceous earth and concentrated by evaporation. The residue was adsorbed onto silica and purified by chromatography eluting with 0-40% EtOAc/isohexane to give the title compound (294 mg, 15%) as an oil; 1H NMR δ 1.18 (6H, t), 1.58-1.71 (4H, m), 1.75 (4H, t), 2.56 (1H, t), 3.89 (4H, q), 4.08-4.20 (4H, m), 4.88 (1H, s), 7.15-7.29 (4H, m); MS m/e MH+ 377.

Workup

  1. customThe reaction mixture was degassed several times
  2. temperatureThe mixture was heated
  3. temperatureunder reflux for 40 h
  4. filtrationthen was filtered through diatomaceous earth
  5. concentrationconcentrated by evaporation
  6. custompurified by chromatography
  7. washeluting with 0-40% EtOAc/isohexane

Sources & evidence

ORD record
ord-415fe447e003464485ad55472030ee28
Source dataset
uspto-grants-2010_09
Patent number
US07795283B2

Reaction notes

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