Formic Acid → Methyl 4-[2-carboxy-4-(4-cyanophenyl)butyl]benzoate

HRID 1913759Notes

Reaction equation

C(N(CC)CC)C.C(O)=O.[C:11]([C:13]1[CH:18]=[CH:17][C:16]([CH2:19][CH2:20][C:21]([CH2:34][C:35]2[CH:40]=[CH:39][C:38]([C:41]([O:43][CH3:44])=[O:42])=[CH:37][CH:36]=2)(C(OCC=C)=O)[C:22]([O:24]CC=C)=[O:23])=[CH:15][CH:14]=1)#[N:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:22]([CH:21]([CH2:20][CH2:19][C:16]1[CH:15]=[CH:14][C:13]([C:11]#[N:12])=[CH:18][CH:17]=1)[CH2:34][C:35]1[CH:40]=[CH:39][C:38]([C:41]([O:43][CH3:44])=[O:42])=[CH:37][CH:36]=1)([OH:24])=[O:23]

Participants

Conditions

Temperature: 10 °C

Procedure

A solution of 41.8 ml (0.3 mol) of triethylamine and 8.6 ml (0.23 mol) of formic acid in 500 ml of dioxane is added to a solution of 43.5 g (0.09 mol) of diallyl 2-[2-(4-cyanophenyl)ethyl]-2-(4-methoxycarbonylbenzyl)malonate, 1.67 g (0.01 mol) of triphenylphosphine and 410 mg of palladium acetate in 505 ml of dioxane at room temperature. The reaction mixture is then stirred at 10° C. for 2 hours. After conversion is complete, the reaction solution is cooled and the solvent is removed in vacuo. The resulting residue is purified by flash chromatography on silica gel (mobile phase: dichloromethane/methanol 50:1). 25 g (74 mmol, 82% yield) of a colourless solid are obtained.

Workup

temperaturethe reaction solution is cooled
customthe solvent is removed in vacuo
customThe resulting residue is purified by flash chromatography on silica gel (mobile phase: dichloromethane/methanol 50:1)

Sources & evidence

ORD record: ord-376a5c823d3f46c5828cfadd3953d283
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08609727B2

Reaction notes

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