Carbamic acid, (5-amino-2-pyridinyl)-, 1,1-dimethylethyl ester (9CI)

tert-Butyl (5-nitropyridin-2-yl)carbamate (1 eq), Pd/C (10percent w/w) and ethyl acetate was added to a flask under H2 atmosphere. The mixture was stirred at room temperature overnight. The mixture was filtered through a celite pad andthe filtrate concentrated under reduced pressure to obtain tert-butyl (5- am inopyridin-2-yl)carbamate.HPLC-MS (method A): Rt= 1.50 mm, [M+H] m/z: 210. Yield: quantitative yield.To 0.314 g (1.31 mmol) of the above nitro compound in THF-MeOH (16 mL, 1:1) was added 0.460 g of 10percent Pd/C and the mixture was stirred under hydrogen (40 in/Hg) for 4 hrs. The reaction mixture was filtered through celite, washed with MeOH and concentrated to give 0.277 g (99percent yield) of tert-butyl 5-aminopyridin-2-yl-carbamate as a white powder: Example 37Synthesis of NPREPARATION 47ferf-Butyl 5-nitropyridin-2-ylcarbamate (4.00 g, 16.72 mmol, Preparation 46) was dissolved in THF/MeOH. Pd/C (2.03 g, 1 .91 mmol) was added and the reaction mixture was stirred under hydrogen atmosphere. The reaction mixture was stirred for a total of 6h. The reaction mixture was filtered and evaporated to yield the desired product as a purple solid (3.40 g, 97percent yield) which was stored at -20 °C.LRMS (m/z): 210 (M+1 )B. Synthesis of N-(5-amino(2-pyridyl))(tert-butoxy)carboxamide (0133) To a suspension of (tert-butoxy)-N-(5-nitro(2-pyridyl))carboxamide (0.27 g, 1.13 mmol) in methanol (2 mL), ethyl acetate (4 mL) and TEA (0.16 mL) was added 10percent Pd/C (60 mg, 0.056 mmol) under argon. The reaction mixture was hydrogenated under 1 atm HSynthesis of compound 223.3. To a suspension of 10percent Pd/C (0.0 lOg) in methanol (5ml) was added 223.2 (0.500g, 2.1mmol, l .Oeq) in M eOH (5mL). Suspension was purged with hydrogen gas for lh at room temperature. Reaction mixture was filtered through celite washed with methanol and obtained filtrate was concentrated under reduced pressure and purified by flash chromatography to get pure 223.3 (0.28 g, 64.0 percent) MS (ES): m/z 209.25 [M+H]A 3-L round-bottomed flask was charged with tert-butyl (5-nitro-2- pyridinyl)carbamate (96.4 g, 403 mmol), 500 mL of MeOH, 500 mL of THF, and 100 mL of sat aq NHA 3-L round-bottomed flask was charged with tert-butyl (5-nitro-2- pyridinyl)carbamate (96.4 g, 403 mmol), 500 mL of MeOH, 500 mL of THF, and 100 mL of sat aq NHStep 1 tert-Butyl (5-((5-chloro-3-cyanopyrazolo[1, 5-a]pyrimidin-7-yl)amino)pyridin-2-yl)carbamate To a solution of 5, 7-dichloropyrazolo[1, 5-a]pyrimidine-3-carbonitrile (240 mg, 1.126 mmol) in NMP (3 mL) at 0 C., was added