(2-methylsulfonylphenyl)boronic acid

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

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: Following the procedure used to prepare 3-(4-(1-aminocyclobutyl)phenyl)-8-(1-isobutyl-1H-pyrazol-4-yl)-2-phenyl-4H-pyrano[2,3-c]pyridin-4-one, tert-butyl (1-(4-(8-chloro-4-oxo-2-phenyl-4H-pyrano[2,3-c]pyridin-3-yl)phenyl)cyclobutyl)carbamate was reacted with (2-(methylsulfonyl)phenyl)boronic acid to give the title compound (40 mg, 62%). LCMS (Method I): RT=7.31 min, [M+2]+=567 (-tBu).

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

Procedure: Following the procedure used to prepare 3-(4-(1-aminocyclobutyl)phenyl)-8-(1-isobutyl-1H-pyrazol-4-yl)-2-phenyl-4H-pyrano[2,3-c]pyridin-4-one, tert-butyl (1-(4-(8-chloro-4-oxo-2-phenyl-4H-pyrano[2,3-c]pyridin-3-yl)phenyl)cyclobutyl)carbamate was reacted with (2-(methylsulfonyl)phenyl)boronic acid to give the title compound (40 mg, 62%). LCMS (Method I): RT=7.31 min, [M+2]+=567 (-tBu).

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 8-Bromo-2-(2-isopropyl-2H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene 194 (0.050 g, 0.13 mmol) and crushed Potassium phosphate (0.0851 g, 0.401 mmol) in N,N-Dimethylformamide (0.5 mL) was thoroughly degassed with N2. 2-Methylsulfonylphenylboronic acid (0.053 g, 0.27 mmol), Palladium Acetate (0.0015 g, 0.0067 mmol) and S-Phos (0.00686 g, 0.0167 mmol) were added and the mixture was heated in the microwave for 30 minutes at 180° C. The reaction was diluted with methylene chloride and filtered through celite. Saturated NH4Cl was added and the mixture was extracted 3 times with methylene chloride. The organic layers were combined, dried with Na2SO4 and concentrated. The crude was purified by reverse-phase HPLC to obtain 8.1 mg of 475 as a white solid. MS (ESI+) 450.1. 1H NMR (400 MHz, DMSO) δ 8.47 (d, J=8.3 Hz, 1H), 8.11 (dd, J=8.0, 1.1 Hz, 1H), 7.98 (s, 1H), 7.92 (s, 1H), 7.79 (td, J=7.5, 1.3 Hz, 1H), 7.70 (td, J=7.8, 1.3 Hz, 1H), 7.45 (dd, J=7.5, 1.1 Hz, 1H), 7.21 (dd, J=8.3, 1.8 Hz, 1H), 7.12 (d, J=1.7 Hz, 1H), 5.93 (hept, J=6.2 Hz, 1H), 4.57 (q, J=5.7 Hz, 4H), 2.93 (s, 3H), 1.50 (d, J=6.6 Hz, 6H) was thoroughly degassed with N2 filtered through celite Saturated NH4Cl was added the mixture was extracted 3 times with methylene chloride dried with Na2SO4 concentrated The crude was purified by reverse-phase HPLC

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

Procedure: Prepared according to the procedure described in Example 84, Step 1, using the following starting materials: {3-[4-bromo-2-(2-oxo-oxazolidin-3-ylmethyl)-phenoxy]-4-methoxy-phenyl}-acetic acid ethyl ester and 2-methylsulfonylphenylboronic acid. Prepared

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

Procedure: According to the Step 22-1 in synthetic method for EXAMPLE 22, compound 105-1 (0.12 g) and 2-methylsulfonylphenylboronic acid (0.11 g) were used instead of 14-4 and 2-thiopheneboronic acid to obtain compound 105-2 (102 mg) as yellow oil.

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of (S)-4-(4,6-dichloro-1,3,5-triazin-2-yl)-3-methylmorpholine (1.25 g, 5.0 mmol), 2-methylsulfonylphenyl boronic acid (1.1 g, 5.5 mmol), sodium carbonate (1.6 g, 15.0 mmol) and bis(triphenylphosphene)palladium(II) dichloride (205 mg, 0.25 mmol) in DME/H2O/ (4:1, 10 mL) was heated in the microwave at 60° C. for 25 minutes. The mixture was then diluted with DCM (200 mL), washed with water (200 mL), the organic layer passed through a PTFE hydrophobic frit and the solvent removed in vacuo to yield a dark orange/brown oil (S)-4-(4-chloro-6-(2-(methylsulfonyl)phenyl)-1,3,5-triazin-2-yl)-3-methylmorpholine, 2.59 g, >100%, crude. washed with water (200 mL) the solvent removed in vacuo

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of (S)-4-(4,6-dichloro-1,3,5-triazin-2-yl)-3-methylmorpholine (1.25 g, 5.0 mmol), 2-methylsulfonylphenyl boronic acid (1.1 g, 5.5 mmol), sodium carbonate (1.6 g, 15.0 mmol) and bis(triphenylphosphene)palladium(II) dichloride (205 mg, 0.25 mmol) in DME/H2O/ (4:1, 10 mL) was heated in the microwave at 60° C. for 25 minutes. The mixture was then diluted with DCM (200 mL), washed with water (200 mL), the organic layer passed through a PTFE hydrophobic frit and the solvent removed in vacuo to yield a dark orange/brown oil (S)-4-(4-chloro-6-(2-(methylsulfonyl)phenyl)-1,3,5-triazin-2-yl)-3-methylmorpholine, 2.59 g, >100%, crude. washed with water (200 mL) the solvent removed in vacuo

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

Procedure: 8-(2-Methanesulfonyl-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-ylamine was prepared from 8-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-ylamine (0.50 g, 2.3 mmol) and 2-(methylsulfonyl)phenylboronic acid (0.56 g, 2.8 mmol) in a manner analogous to Step 2c. The reaction product was isolated as a pale yellow solid (0.249 g, 37%). 1H NMR (400 MHz, (D3C)2SO, δ, ppm): 8.56 (d, J=6.6 Hz, 1H), 8.10 (d, J=7.8 Hz, 1H), 7.79 (t, J=7.6 Hz, 1H), 7.73 (d, J=7.7 Hz, 1H), 7.48 (d, J=7.3 Hz, 1H), 7.36 (d, J=7.1 Hz, 1H), 6.93 (d, J=6.9 Hz, 1H), 5.99 (s, 2H), 3.16 (s, 3H). MS=289 (MH)+.

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

Procedure: 8-(2-Methanesulfonyl-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-ylamine was prepared from 8-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-ylamine (0.50 g, 2.3 mmol) and 2-(methylsulfonyl)phenylboronic acid (0.56 g, 2.8 mmol) in a manner analogous to Step 2c. The reaction product was isolated as a pale yellow solid (0.249 g, 37%). 1H NMR (400 MHz, (D3C)2SO, δ, ppm): 8.56 (d, J=6.6 Hz, 1H), 8.10 (d, J=7.8 Hz, 1H), 7.79 (t, J=7.6 Hz, 1H), 7.73 (d, J=7.7 Hz, 1H), 7.48 (d, J=7.3 Hz, 1H), 7.36 (d, J=7.1 Hz, 1H), 6.93 (d, J=6.9 Hz, 1H), 5.99 (s, 2H), 3.16 (s, 3H). MS=289 (MH)+.