Dichloromethane → Tert-butyl [2-(6-acetyl-4-chloro-3-cyano-2-vinylphenoxy)ethyl]carbamate

HRID 626836Notes

Reaction equation

[C:1]([C:4]1[C:9]([O:10][CH2:11][CH2:12][NH:13][C:14](=[O:20])[O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[C:8](I)[C:7]([C:22]#[N:23])=[C:6]([Cl:24])[CH:5]=1)(=[O:3])[CH3:2].[CH3:25][C:26]1(C)C(C)(C)OB(C=C)O1.ClCCl.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.O>[C:1]([C:4]1[C:9]([O:10][CH2:11][CH2:12][NH:13][C:14](=[O:20])[O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[C:8]([CH:25]=[CH2:26])[C:7]([C:22]#[N:23])=[C:6]([Cl:24])[CH:5]=1)(=[O:3])[CH3:2]

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of tert-butyl [2-(6-acetyl-4-chloro-3-cyano-2-iodophenoxy)ethyl]carbamate (3.3 g, 7.1 mmol), 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane (1.81 mL, 10.6 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (1:1) (0.3 g, 0.4 mmol) and potassium carbonate (2.9 g, 21 mmol) in 1,4-dioxane (40 mL) and water (20 mL) was degassed with nitrogen. The resulting mixture was heated at 80° C. for 1 h. The mixture was poured into water and extracted with ethyl acetate. The extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated. The product was purified by FCC on silica gel using ethyl acetate in hexane (0-40%) to give the desired compound tert-butyl [2-(6-acetyl-4-chloro-3-cyano-2-vinylphenoxy)ethyl]carbamate as a crystalline solid (2.2 g. 85%). LCMS calculated for C18H21ClIN2O4Na (M+Na)+: m/z=387.1; found: 387.0.

Workup

customwas degassed with nitrogen
additionThe mixture was poured into water
extractionextracted with ethyl acetate
washThe extracts were washed with brine
dry with materialdried over magnesium sulfate
filtrationfiltered
concentrationconcentrated
customThe product was purified by FCC on silica gel

Sources & evidence

ORD record: ord-4811960b75564d77b66e4533599edf99
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09309251B2

Reaction notes

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