Triethylamine → Ethyl (4-fluorophenyl)-[4-{isopropoxy}-3-vinylphenyl]-phosphinate

HRID 448836Notes

Reaction equation

[F:1][C:2]1[CH:7]=[CH:6][C:5]([PH:8](=[O:10])[O-:9])=[CH:4][CH:3]=1.Br[C:12]1[CH:17]=[CH:16][C:15]([O:18][CH:19]([CH3:21])[CH3:20])=[C:14]([CH:22]=[CH2:23])[CH:13]=1.[CH2:24](N(CC)CC)[CH3:25]>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[F:1][C:2]1[CH:7]=[CH:6][C:5]([P:8]([C:12]2[CH:17]=[CH:16][C:15]([O:18][CH:19]([CH3:21])[CH3:20])=[C:14]([CH:22]=[CH2:23])[CH:13]=2)(=[O:9])[O:10][CH2:24][CH3:25])=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 68 °C

Procedure

To a degassed mixture of 4-fluoro-phenylphosphinate AZ2 (2.07 g, 11.0 mmol) and 4-bromo-1-isopropoxy-2-vinylbenzene (2.43 g, 10.0 mmol) in acetonitrile (66 mL) were added triethylamine (3.1 mL, 22.0 mmol), palladium acetate (112 mg, 0.5 mmol), and 1,1′-bis(diphenylphosphino)ferrocene (277 mg, 0.5 mmol). The mixture was heated at 68° C. for 24 hrs. The volatiles were removed in vacuo, and the residue was purified by column chromatography using 40 to 80% ethyl acetate in petroleum ether to afford 2.84 g of compound BA2 in 82% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.36 (d, J=6.0 Hz, 6H), 1.38 (t, J=7.1 Hz, 3H), 4.02-4.15 (m, 2H), 4.62 (sept., J=6.0 Hz, 1H), 5.29 (dd, J=11.2 and 1.1 Hz, 1H), 5.78 (dd, J=17.7 and 1.4 Hz, 1H), 6.91 (dd, J=8.7 and 3.0 Hz, 1H), 6.99 (dd, J=17.4 and 10.9 Hz, 1H), 7.12 (td, J=8.8 and 2.5 Hz, 2H), 7.61 (ddd, J=11.7, 8.6 and 1.9 Hz, 1H), 7.75-7.84 (m, 2H), 7.88 (dd, J=12.5 and 1.9 Hz, 1H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 30.71.

Workup

customThe volatiles were removed in vacuo
customthe residue was purified by column chromatography

Sources & evidence

ORD record: ord-db26036f9c814bb8ac5f1d6bf818ddca
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08481748B2

Reaction notes

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