tert-Butyl acrylate → (E)-tert-Butyl 3-(2-(2-ethoxy-2-oxoethyl)phenyl)acrylate

HRID 84955

Reaction equation

Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])(=[O:17])[CH:15]=[CH2:16].C1(C(N)C2CCCCC2)CCCCC1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C>[CH2:12]([O:11][C:9](=[O:10])[CH2:8][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1/[CH:16]=[CH:15]/[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH3:13]

Participants

Conditions

Temperature: 70 °C

Procedure

To a mixture of ethyl 2-(2-bromophenyl)acetate (0.97 g, 4 mmol), t-butyl acrylate (0.51 g, 4 mmol), tris(dibenzylideneacetone)dipalladium(0) (91 mg, 0.1 mmol), dicyclohexylmethylamine (0.98 g, 5 mmol) in dioxane (5 mL) was added tri-tert-butylphosphine (0.2 mL, 1 N in toluene, 0.2 mmol). The mixture was heated at 70° C. for 30 minutes under N2. Ethyl acetate was added, and the mixture was filtered through diatomaceous earth. The filtrate was concentrated and purified by silica gel column chromatography eluting with hexanes and ethyl acetate (10:1) to afford the title compound. 1H NMR (300 MHz, DMSO-d6) δ ppm 7.79 (m, 1H), 7.72 (d, J=15.6 Hz, 1H), 7.34 (m, 3H), 6.40 (d, J=15.7 Hz, 1H), 4.06 (q, J=7.2 Hz, 2H), 3.84 (s, 2H), 1.48 (s, 9H), and 1.17 (t, J=2 Hz, 3H).

Workup

filtrationthe mixture was filtered through diatomaceous earth
concentrationThe filtrate was concentrated
custompurified by silica gel column chromatography
washeluting with hexanes and ethyl acetate (10:1)

Sources & evidence

ORD record: ord-02bb524d6400491e80253008d44c0ca7
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08846951B2

Linked notes

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