Dichloromethane → Tert-butyl 1-(2-methylprop-1-enyl)-4-nitrobenzene

HRID 522668Notes

Reaction equation

I[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[CH3:11][C:12]1([CH3:23])[C:16](C)(C)OB(C=C(C)C)O1.C(=O)(O)[O-].[Na+].ClCCl>O1CCOCC1.O.CC(=O)OCC>[C:12]([C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[CH:11]=[C:12]([CH3:23])[CH3:16])([CH3:23])([CH3:16])[CH3:11]

Participants

Conditions

Temperature: 90 °C

Procedure

A mixture of 1-iodo-4-nitrobenzene (2.49 g, 10.0 mmol), 4,4,5,5-tetramethyl-2-(2-methylprop-1-enyl)-1,3,2-dioxaborolane (1.82 g, 10.0 mmol), sodium bicarbonate (2.52 g, 30.0 mmol) and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (816 mg, 1.0 mmol) in dioxane/water (5:1, 60 mL) was stirred at 90° C. for 20 h under N2. LCMS and TLC monitored the reaction was completed. The reaction mixture was cooled to RT and concentrated. The residue was dissolved in 100 mL of EtOAc, washed with water (150 mL×3) and brine, dried over Na2SO4, filtered and concentrated under vacuo. The crude product was purified by silica gel column, eluting with PE:EA (6:1), to obtain the desired product (1.9 g, 100% yield) as a yellow oil, 1H-NMR (400 MHz, CDCl3) δ ppm 8.17 (d, 2H, J=8.8 Hz), 7.35 (d, 2H, J=8.8 Hz), 6.36 (s, 1H), 1.96 (d, 3H, J=0.4 Hz), 1.90 (d, 3H, J=0.4 Hz).

Workup

temperatureThe reaction mixture was cooled to RT
concentrationconcentrated
dissolutionThe residue was dissolved in 100 mL of EtOAc
washwashed with water (150 mL×3) and brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated under vacuo
customThe crude product was purified by silica gel column
washeluting with PE

Sources & evidence

ORD record: ord-fb96f7d564e545849d5ec344401d84f0
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09334263B2

Reaction notes

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