4-tri(propan-2-yl)silyloxyaniline

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-[[tris(propan-2-yl)silyl]oxy]aniline (15 g, 56 mmol) in toluene (100 ml) was added 4-bromo-1-nitro-2-(trifluoromethyl)benzene (22.84 g, 84.6 mmol, 1.5 eq.), Pd2(dba)3 (2.34 g, 2.3 mmol, 4 mol %), BINAP (710 mg, 1.1 mmol, 2 mol %) and t-BuONa (10.87 g, 113.2 mmol, 2 eq.). The mixture was stirred under nitrogen overnight at 100° C. (oil bath). The reaction mixture was concentrated under vacuum to give a residue, which was purified by silica gel column chromatography using 10% ethyl acetate in petroleum ether to afford 4-nitro-3-(trifluoromethyl)-N-(4-[[tris(propan-2-yl)silyl]oxy]phenyl)aniline as a orange solid (8 g, 31%); (ES, m/z): [M+H]+ 455; 1H NMR (300 MHz, CDCl3): δ 7.97 (d, J=6.0 Hz, 1H), 7.05-7.09 (m, 3H), 6.87-6.96 (m, 3H), 6.18 (s, 1H), 1.26-1.33 (m, 3H), 1.13 (s, 18H). The reaction mixture was concentrated under vacuum to give a residue, which was purified by silica gel column chromatography

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

Procedure: To a solution of 4-aminophenol (20 g, 183 mmol) in dichloromethane (300 ml) was added 1H-imidazole (16.2 g, 240 mmol, 1.3 eq.). Triisopropyl chlorosilane (53.1 g, 275 mmol, 1.5 eq.) was added dropwise with stirring for 2 hours at room temperature. The reaction mixture was filtered and the filtrate was concentrated under vacuum to give a residue, which was purified by silica gel column chromatography using 25% ethyl acetate in petroleum ether to afford 4-[[tris(propan-2-yl)silyl]oxy]aniline as brown oil (34 g, 70%); (ES, m/z): [M+H]+ 266; 1H NMR (300 MHz, CDCl3): δ 6.66-6.72 (m, 2H), 6.55-6.59 (m, 2H), 3.23 (s, 2H), 1.20-1.30 (m, 3H), 1.13 (s, 18H). The reaction mixture was filtered the filtrate was concentrated under vacuum to give a residue, which was purified by silica gel column chromatography