Dichloromethane → tert-Butyl [2-(6-acetyl-4-chloro-3-methyl-2-vinylphenoxy)ethyl]carbamate

HRID 626814Notes

Reaction equation

HRID 626814 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](Br)[C:7]([CH3:22])=[C:6]([Cl:23])[CH:5]=1)(=[O:3])[CH3:2].[CH3:24][C:25]1(C)C(C)(C)OB(C=C)O1.ClCCl.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.Cl[Pd]Cl.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].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:24]=[CH2:25])[C:7]([CH3:22])=[C:6]([Cl:23])[CH:5]=1)(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 52330122-Ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 86697510tert-Butyl [2-(6-acetyl-2-bromo-4-chloro-3-methylphenoxy)ethyl]carbamate

Product 1

HCID 86697511tert-Butyl [2-(6-acetyl-4-chloro-3-methyl-2-vinylphenoxy)ethyl]carbamateYield 72.4%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of tert-butyl [2-(6-acetyl-2-bromo-4-chloro-3-methylphenoxy)ethyl]carbamate (6.5 g, 16 mmol), 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane (3.3 mL, 19 mmol), [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II), complex with dichloromethane (1:1) (600 mg, 0.8 mmol) and potassium carbonate (6.6 g, 48 mmol) in 1,4-dioxane (100 mL), and water (50 mL) was heated at 80° C. for 3 hours and 50° C. overnight. The reaction mixture was cooled to room temperature and extracted with ethyl acetate (3×10 mL). The organic layers were combined and washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified on a silica gel with ethyl acetate in hexanes (0-25%) to afford the desired compound (4.1 g, 72%). LCMS calculated for C18H24ClNO4Na (M+Na)+: m/z=376.1; found: 376.0.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. extractionextracted with ethyl acetate (3×10 mL)
  3. washwashed with brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified on a silica gel with ethyl acetate in hexanes (0-25%)

Sources & evidence

ORD record
ord-55530c38d12d43f886b1a096d7e1afd8
Source dataset
uspto-grants-2016_04
Patent number
US09309251B2

Reaction notes

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