N-[2-(2-bromophenyl)ethyl]-2,2,2-trifluoroacetamide

Conditions: temp:50.01; pressure:0.00; stir:

Procedure: Following general procedure F using 4f (74 mg, 0.25 mmol), B2pin2 (127 mg, 0.50 mmol), [Ir(COD)OMe]2 (2.5 mg, 0.00375 mmol) and dtbpy (2.0 mg, 0.0075 mmol) in THF (1.25 mL). Stirred in vial at 50 °C for 20 hours. Analysis of crude 1 H NMR using internal standard 1,2‐dimethoxyethane showed 1:1.7 meta:para borylation in 92% yield. The crude product was purified by silica gel chromatography (15% EtOAc in Petroleum Ether 40‐60 o C) gave the title compound (as a 1:1.8 mixture of meta:para ratio, as determined by 1 H NMR) as a colourless oil (103 mg). A small amount of B2Pin2 impurity was found to be inseparable from the final product on silica. Corrected yield ‐ 100 mg, 0.23 mmol, 94%. By subtracting the resonances for the meta isomer, the NMR data of the para isomer can be assigned as follows:

Conditions: temp:50.01; pressure:0.00; stir:

Procedure: Following general procedure F using 4f (74 mg, 0.25 mmol), B2pin2 (127 mg, 0.50 mmol), [Ir(COD)OMe]2 (2.5 mg, 0.00375 mmol) and 1a (3.8 mg, 0.0075 mmol) in THF (1.25 mL). Stirred in vial at 50 °C for 20 hours. Analysis of crude 1 H NMR using internal standard 1,2‐dimethoxyethane showed 8.0:1 meta:para borylation in 93% yield. The crude product was purified by silica gel chromatography (15% EtOAc in Petroleum Ether 40‐60 o C) gave the title compound (as a 7.2:1 mixture of meta:para ratio, as determined by 1 H NMR) as a white solid (103 mg). A small amount of B2Pin2 impurity was found to be inseparable from the final product on silica. Corrected yield ‐ 96 mg, 0.23 mmol, 91%.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of N-(2-bromophenethyl)-2,2,2-trifluoroacetamide (8.88 g, 30 mmol) and paraformaldehyde (13.5 g, 0.45 mol) in 45 mL of glacial acetic acid at room temperature was slowly added 30 mL of sulfuric acid (96.6%). After stirring at room temperature overnight, the reaction mixture was quenched with ice water and extracted with EtOAc, washed with brine and Sat. NaHCO3 and dried over Na2SO4. After concentration, flash chomatography (SiO2, hexane/DCM=1:1) gave of 1-(5-bromo-3,4-dihydroisoquinolin-2(1H)-yl)-2,2,2-trifluoroethanone as a white solid. the reaction mixture was quenched with ice water extracted with EtOAc washed with brine and Sat. NaHCO3 dried over Na2SO4 After concentration, flash chomatography (SiO2, hexane/DCM=1:1)