Formic Acid → Methyl 4-[3-carboxy-4-(3,5-difluoro-4-triisopropylsilanyloxyphenyl)butyl]benzoate

HRID 1921884Notes

Reaction equation

[F:1][C:2]1[CH:3]=[C:4]([CH:31]=[C:32]([F:45])[C:33]=1[O:34][Si:35]([CH:42]([CH3:44])[CH3:43])([CH:39]([CH3:41])[CH3:40])[CH:36]([CH3:38])[CH3:37])[CH2:5][C:6]([CH2:19][CH2:20][C:21]1[CH:26]=[CH:25][C:24]([C:27]([O:29][CH3:30])=[O:28])=[CH:23][CH:22]=1)(C(OCC=C)=O)[C:7]([O:9]CC=C)=[O:8].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.C(O)=O>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:7]([CH:6]([CH2:5][C:4]1[CH:3]=[C:2]([F:1])[C:33]([O:34][Si:35]([CH:39]([CH3:41])[CH3:40])([CH:42]([CH3:44])[CH3:43])[CH:36]([CH3:37])[CH3:38])=[C:32]([F:45])[CH:31]=1)[CH2:19][CH2:20][C:21]1[CH:22]=[CH:23][C:24]([C:27]([O:29][CH3:30])=[O:28])=[CH:25][CH:26]=1)([OH:9])=[O:8]

Participants

Conditions

Temperature: 100 °C

Procedure

9.2 g (14.27 mmol) of diallyl 2-(3,5-difluoro-4-triisopropylsilanyloxybenzyl)-2-[2-(4-methoxycarbonylphenyl)ethyl]malonate, 64 mg (0.29 mmol) of palladium(II) acetate and 262 mg (1 mmol) of triphenylphosphine are stirred in 300 ml of dioxane under argon. Then a solution of 4.76 g (47.08 mmol) of triethylamine and 1.64 g (35.67 mmol) of formic acid in 200 ml of dioxane is added dropwise, and the mixture is heated at 100° C. for 2 h. The cooled mixture is concentrated and the crude product is chromatographed on silica gel (mobile phase: cyclohexane/ethyl acetate 10:1→4:1). 3.69 g (49% of theory) of the title compound are obtained.

Workup

concentrationThe cooled mixture is concentrated
customthe crude product is chromatographed on silica gel (mobile phase: cyclohexane/ethyl acetate 10:1→4:1)

Sources & evidence

ORD record: ord-b650bceeaf26401da6eb135a3095c37f
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08173704B2

Reaction notes

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