3-BROMO-4-FLUOROPYRIDINE

To a solution of 3-bromo-4-fluoro-pyridine (300.0 mg, 1.70 mmol) in THF (10 mL) was added dropwise n-BuLi (1.02 mL, 2.55 mmol) at -78 C under N2. After stirred for 30 minute at -78 C, triisopropyl borate (376 mg, 2.0 mmol) was added. The reaction mixture was warmed to room temperature and stirred for another 30 minute. The reaction mixture was quenched with Sat. NH4Cl (5 mL) and extracted with DCM (10 mL x3). The combined aqueous layers were concentrated in vacuum. The residue was purified by flash chromatography (ACN/H20: 5% to 95 %) to give 4-fluoropyridine-3-boronic acid (240 mg, yield: 100 %) as a yellow oil. MS: m/z 142.0 (M+H+).General procedure: E3 (1.0 equivalents), bis-(pinacolato)diboron, (1.5 equivalents, CAS: 73183-34-3), tris(dibenzylideneacetone)dipalladium(0) Pd2(dba)3 (0.04 equivalents, CAS: 51364-51-3), X-Phos (0.04 equivalents, CAS 564483-18-7) and potassium acetate (KOAc, 3.0 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110 00 for 16 h. After cooling down to room temperature (RT) the reaction mixture is extracted with ethyl acetate/brine. The organic phases are collected, washed with brine and dried over MgSO4. The organic solvent is removed, the crude product E4 is purified by chromatography and obtained as a white solid.2-(3-Bromo-4-fluorophenyl)-4, 6-diphenyl-1 , 3, 5-triazine E2 (1.0 equivalents), bis- (pinacolato)diboron, (1 .5 equivalents, CAS: 73183-34-3), tris(dibenzylideneacetone)dipalladium(0) Pd2(dba)3 (0.02 equivalents, CAS: 51364-51 -3), X- Phos (0.04 equivalents, CAS 564483-18-7) and potassium acetate (KOAc, 3.0 equivalents) are stirred under nitrogen atmosphere in dry toluene at 1 10 C for 16 h. After that time, 3- bromo-4-fluoropyridine (1 .0 equivalents, CAS 1 16922-60-2), K3P04 (aq) (3 equivalents) and extra portion of tris(dibenzylideneacetone)dipalladium(0) (0.02 equivalents, CAS: 51364-51 -3) and X-Phos (0.04 equivalents CAS 564483-18-7) are added to the hot reaction mixture. The reaction mixture is stirred at 1 10 C for 16 h. After cooling down to room temperature (RT) the reaction mixture is extracted with ethyl acetate/brine. The organic phases are collected, washed with brine and dried over MgSC . The organic solvent is removed, the crude product Z2 is purified by chromatography and obtained as a white solid (yield: 86 %).

Molecular Weight:175.99
XLogP3:1.6
Hydrogen Bond Acceptor Count:2
Exact Mass:174.94329
Monoisotopic Mass:174.94329
Topological Polar Surface Area:12.9
Heavy Atom Count:8
Complexity:78.8
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes