Tri-o-tolylphosphine → Phenylmethyl 4-ethenyl-1H-pyrazole-1-carboxylate

HRID 660496Notes

Reaction equation

[CH2:1]([O:8][C:9]([N:11]1[CH:15]=[C:14](I)[CH:13]=[N:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:17][C:18]1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(C([Sn])=C(CCCC)CCCC)CCC.[F-].[K+]>CC#N.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:1]([O:8][C:9]([N:11]1[CH:15]=[C:14]([CH:17]=[CH2:18])[CH:13]=[N:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 4-iodopyrazole-1-carboxylic acid benzyl ester (2.03 g, 6.20 mmol), Pd2(dba)3 (120 mg, 0.131 mmol), P(o-tolyl)3 (283 mg, 0.929 mmol) and tributylvinyltin (2.71 mL, 9.28 mmol) in CH3CN (15 ml) is heated at 80° C. for 3 h. The mixture is cooled to RT, stirred with aq. KF for 15 min and filtered through Celite. The filtrate is partitioned between EtOAc and brine. The organic layer is dried over MgSO4, concentrated and chromatographed to afford the title compound as a light yellow solid: 1H NMR (CDCl3) δ 8.06 (s, 1H), 7.84 (s, 1H), 7.50-7.32 (m, 5H), 6.51 (dd, J=16.0, 12.0 Hz, 1H), 5.60 (d, J=16.0 Hz, 1H), 5.46 (s, 2H), 5.26 (d, J=12.0 Hz, 1H).

Workup

temperatureThe mixture is cooled to RT
filtrationfiltered through Celite
customThe filtrate is partitioned between EtOAc and brine
dry with materialThe organic layer is dried over MgSO4
concentrationconcentrated
customchromatographed

Sources & evidence

ORD record: ord-34b340c4f63643979a2b340402328940
Source dataset: uspto-grants-2011_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08084448B2

Reaction notes

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