Pinacol → 2-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile

HRID 1396534Notes

Reaction equation

[F:1][C:2]1[CH:3]=[C:4]([B:10]([OH:12])[OH:11])[CH:5]=[CH:6][C:7]=1[C:8]#[N:9].O[C:14]([C:17](O)([CH3:19])[CH3:18])([CH3:16])[CH3:15]>C1CCCCC1>[F:1][C:2]1[CH:3]=[C:4]([B:10]2[O:12][C:17]([CH3:19])([CH3:18])[C:14]([CH3:16])([CH3:15])[O:11]2)[CH:5]=[CH:6][C:7]=1[C:8]#[N:9]

Participants

Conditions

Temperature: 40 °C

Procedure

A suspension of the crude 3-fluoro-4-cyanophenyl boronic acid (9.2 Kg, 55.8 mol) in cyclohexane (150 L) was treated with pinacol (13.2 Kg, 111.6 mol, 2.0 equiv) at room temperature, and the resulting reaction mixture was warmed to 40° C. for 4 h. When TLC and LC/MS showed that the reaction was deemed complete, the reaction mixture was cooled down to room temperature before being washed with water (2×75 L). The organic layer was then dried over magnesium sulfate (MgSO4) and concentrated under the reduced pressure to afford 2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (19, 11.8 Kg, 13.8 Kg theoretical, 85.6% yield) as a light yellow solid. For 19: 1H NMR (300 MHz, DMSO-d6) δ ppm 7.92 (t, 1H, J=7.00 Hz), 7.62 (m, 2H), 1.29 (s, 12H).

Workup

customthe resulting reaction mixture
temperaturethe reaction mixture was cooled down to room temperature
washbefore being washed with water (2×75 L)
dry with materialThe organic layer was then dried over magnesium sulfate (MgSO4)
concentrationconcentrated under the reduced pressure

Sources & evidence

ORD record: ord-5006a6a9c26b4d71ae57c5ea0b9f1068
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08901123B2

Reaction notes

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