1-Cyclohexenylboronic acid → 4-(1-Cyclohexen-1-yl)-3-ethylbenzonitrile

HRID 423307Notes

Reaction equation

[CH2:1]([C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1I)[C:6]#[N:7])[CH3:2].[C:12]1(B(O)O)[CH2:17][CH2:16][CH2:15][CH2:14][CH:13]=1.C[O-].[Na+]>CO.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[C:12]1([C:10]2[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=2[CH2:1][CH3:2])[CH2:17][CH2:16][CH2:15][CH2:14][CH:13]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 3-ethyl-4-iodobenzonitrile (D16) (1.23 g, 4.80 mmol), 1-cyclohexen-1-ylboronic acid (907 mg, 7.20 mmol), sodium methoxide (778 mg, 14.4 mmol) and bis(triphenylphosphine)palladium (II) chloride (337 mg, 0.48 mmol) in anhydrous methanol (12 mL) was heated at 80° C. for 10 minutes in the microwave. The reaction mixture was partitioned between ethyl acetate (40 mL) and water (40 mL) before the organic layer was further washed with water (40 mL), dried (phase separator) and concentrated in vacuo. The crude material was purified by silica chromatography, eluting 0-5% EtOAc in hexane over 30 minutes to give the title compound as a yellow oil (824 mg, 3.91 mmol). δH (methanol-d4, 400 MHz) 7.56 (1H, d), 7.46 (1H, dd), 7.19 (1H, d), 5.61-5.56 (1H, m), 2.68 (2H, quart), 2.23-2.16 (4H, m), 1.85-1.68 (4H, m), 1.20 (3H, t). MS (ES): No mass ion observed.

Workup

customThe reaction mixture was partitioned between ethyl acetate (40 mL) and water (40 mL) before the organic layer
washwas further washed with water (40 mL)
customdried (phase separator)
concentrationconcentrated in vacuo
customThe crude material was purified by silica chromatography
washeluting 0-5% EtOAc in hexane over 30 minutes

Sources & evidence

ORD record: ord-1d9f5b25ad2a400f87a38c8917aa6a69
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08101775B2

Reaction notes

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