3-ethenyl-1-hydroxy-3H-2,1-benzoxaborole

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The mixture of 3-vinylbenzo[c][1,2]oxaborol-1(3H)-ol (2.2 g, 13.4 mmol, 1.3 eq), 2-bromo-5-chloro-N-(5-cyclopropyl-1H-pyrazol-3-yl)pyrimidin-4-amine (3.3 g, 10.5 mmol, 1.0 eq), Pd(PPh3)4 (1.3 g, 1.1 mmol, 0.11 equiv.) and saturated aq Na2CO3 (5 mL) in 1,4-dioxane (30 mL) was stirred at 90° C. for 3 h under N2, then, cooled to rt and partitioned between EtOAc and water. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to give 1-(2-(5-chloro-4-(5-cyclopropyl-1H-pyrazol-3-ylamino)pyrimidin-2-yl)phenyl)prop-2-en-1-ol (1.8 g, 47%). LC-MS (m/z)=368.0 [M+H]+. cooled to rt partitioned between EtOAc and water The organic layer was washed with brine dried over Na2SO4 filtered concentrated The residue was purified by column chromatography

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of NaH (1.23 g, 28.2 mmol, 1.2 equiv., 60% content) in THF (10 mL) was added a solution of 1-(2-bromophenyl)prop-2-en-1-ol (5.0 g, 23.5 mmol, 1.0 eq) in THF (10 mL) dropwise at 0° C. The mixture was stirred for 1 h, then, cooled to −70° C. n-BuLi (11.3 mL, 28.2 mmol, 1.2 eq., 2.5M in THF) was added. The mixture was stirred for 1 h, then, triisopropyl borate (5.3 g, 28.2 mmol, 1.2 equiv.) was added. The mixture was stirred for 5 h, then, quenched with 2N H2SO4. The mixture was partitioned between brine and ethylacetate. The organic layer was washed over brine, dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to yield 3-vinylbenzo[c][1,2]oxaborol-1(3H)-ol (2.2 g, 57%). LC-MS (m/z)=158.9, 160.9 [M+H]+. was added The mixture was stirred for 1 h The mixture was stirred for 5 h quenched with 2N H2SO4 The mixture was partitioned between brine and ethylacetate The organic layer was washed over brine dried over Na2SO4 filtered concentrated The residue was purified by column chromatography