1-bromo-2-(2-methylpropylsulfonyl)benzene

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

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

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

Procedure: To a solution of 1-bromo-2-isobutylsulfanyl-benzene (8.0 g, 32.6 mmol, 1.0 eq) in DCM (100 mL) at 0° C. was added CaCO3 (13.05 g, 130.4 mmol, 4.0 eq.) and MCPBA (28.1 g, 81.5 mmol, 2.5 eq.). The mixture was stirred for about 30 minutes and filtered through a pad of celite. The solution was washed with sodium bisulfite (2×) and 5N NaOH (2×). The organic layer was dried (Na2SO4), filtered and concentrated. Purification by flash chromatography (250 g SiO2, linear gradient, 40 mL/min, 10%-40% EtOAC/hexane for about 33 minutes) afforded 1-bromo-2-(2-methyl-propane-1-sulfonyl)-benzene (7.4 g, 26.6 mmol, 82%). GCMS (EI): 276.0. 1-bromo-2-(2-methyl-propane-1-sulfonyl)-benzene was coupled to piperazine in a manner similar to Preparation 1A. LRMS (ESI+): 283.06 (M+1)

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

Procedure: The title compound was prepared using analogous conditions to those described in Example 1 utilizing 5-(2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazin-2-amine and 1-bromo-2-(isobutylsulfonyl)benzene. MS (ESI): mass calcd. for C20H20FN3O2S, 385.13; m/z found, 386.2 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ 8.42 (s, 1H), 8.12 (dd, J=7.9, 1.1, 1H), 8.05 (d, J=1.4, 1H), 7.96 (m, 1H), 7.81 (m, 1H), 7.73 (m, 1H), 7.49 (dd, J=7.5, 1.0, 1H), 7.37 (dd, J=12.4, 1.5, 1H), 7.32 (dd, J=8.0, 1.6, 1H), 6.76 (s, 2H), 2.81 (d, J=6.4, 2H), 1.85-1.75 (m, 1H), 0.82 (d, J=6.7, 6H).