1-(Benzenesulfonyl)-1H-pyrrolo[2,3-b]pyridine-3-boronic acid pinacol ester

A solution of 3-iodo-1-(phenylsulfonyl)-1 H-pyrrolo[2, 3-b]pyridine (4.2 g , 10.9 mmol), bis-pinacolatodiboron (5.6 g, 21.8 mmol), potassium acetate (3.2 g, 32.7 mmol) and Pd(dppf)CIA mixture of compound Id (50.78 g), bis(pinacolato)diboron (42.22 g), [l, r-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1:1 complex with dichloromethane, 12.32 g) and potassium acetate (44.46 g) in THF (3OO mL) was refluxed for 24 hrs. The. reaction was quenched with water and extracted, with ethyl acetate. The combined organic phase was concentrated and the residue was purified on silica gel column (eluted with 100percent dichloromethane and 2percent methanol in dichloromethane) to provide l-benzenesulfonyl-3-(4, 4, 5, 5-tetramethyl-[l, 3, 2]dioxaborolan-2-yl)-lH-pyrrolo[2, 3-b]pyridine (Ie) (22.10 g, 38percent) as a white solid. [00248] A suspension of tert-butyl (3/:?)-4-(5-chloro-2-iodo-6-oxo-1 H-pyrimidin-4-yl)-3- methyl-piperazine-1 -carboxylate (3-013) (0.100 g, 0.220 mmol), 1 -(phenylsulfonyl)-7- azaindole-3-boronic acid pinacol ester (0.089 g, 0.231 mmol), cesium carbonate (0.107 g, 0.330 mmol) and tetrakis(triphenylphosphine)palladium (0.013 g, 0.01 1 mmol) in 1 , 4-dioxane (1 mL) and water (0.3 mL) was prepared, degassed, and heated to 80 eC for 1 h. The reaction mixture was partitioned between NaHC03 (sat. aq) and CH2CI2. The organic phase was separated and the aqueous extracted with CH2CI2. The combined organic portions were dried over MgS04, filtered and concentrated by rotary evaporation. The residue was purified by column chromatography on silica gel, eluting with cyclohexane containing 5-50% EtOAc. The appropriate fractions were combined and concentrated to the title compound (0.050 g, 39%) as a colourless solid. LCMS: RT 3.33 min, Ml 585, Method (1 LCMS13); NMR (600 MHz, DMSO-ck) delta 12.82 (s, 1 H), 9.15 (s, 1 H), 8.60 (d, J = 7.9 Hz, 1 H), 8.47 (dd, J = 4.9, 1 .6 Hz, 1 H), 8.16 - 8.15 (m, 2H), 7.78 - 7.75 (m, 1 H), 7.66 (t, J = 7.9 Hz, 2H), 7.50 (dd, J = 8.0, 4.8 Hz, 1 H), 4.47 (br s, 1 H), 4.04 - 3.99 (m, 2H), 3.78 (dt, J = 13.2, 2.1 Hz, 1 H), 3.35 - 3.30 (m, 1 H), 3.20 - 2.95 (br m, 2H), 1 .41 (s, 9H), 1 .21 (d, J = 6.7 Hz, 3H).

Molecular Weight:384.3
Hydrogen Bond Acceptor Count:5
Rotatable Bond Count:3
Exact Mass:384.1315085
Monoisotopic Mass:384.1315085
Topological Polar Surface Area:78.8
Heavy Atom Count:27
Complexity:641
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes