反应详情

To {4-[(methylsulfonyl)amino]phenyl}boronic acid (commercially available from e.g. Combi-Blocks) (127 mg, 0.29 mmol) in dichloromethane (3 ml) was added copper(II) acetate (107 mg, 0.59 mmol) and 4 Å molecular sieves (190 mg), and the reaction stirred at room temperature, open to air, for 10 minutes. 1,1-Dimethylethyl 4,5,7,8-tetrahydropyrazolo[3,4-d]azepine-6(2H)-carboxylate (may be prepared as described in Description 9) (70 mg, 0.29 mmol) was added and the reaction stirred at room temperature, open to air, overnight. The reaction mixture was diluted with methanol and filtered through a celite pad, washing with methanol. Solvent was evaporated in vacuo. Ethyl acetate and water were added, and the product was extracted into ethyl acetate (×3), washed with water (×1), then saturated sodium bicarbonate solution (×1), and then dried over magnesium sulfate. Solvent was evaporated in vacuo. The resulting crude product was purified by column chromatography on silica gel, eluting with a mixture of ethyl acetate in hexane (0-50%). Relevant fractions were combined and solvent evaporated in vacuo. The resulting crude product was purified further by Mass Directed Autopreparation to afford the title compound (D39). MS (ES+) m/e 407 [M+H]+.

1. stirringthe reaction stirred at room temperature, open to air, overnight
2. filtrationfiltered through a celite pad
3. washwashing with methanol
4. customSolvent was evaporated in vacuo
5. additionEthyl acetate and water were added
6. extractionthe product was extracted into ethyl acetate (×3)
7. washwashed with water (×1)
8. dry with materialsaturated sodium bicarbonate solution (×1), and then dried over magnesium sulfate
9. customSolvent was evaporated in vacuo
10. customThe resulting crude product was purified by column chromatography on silica gel
11. washeluting with a mixture of ethyl acetate in hexane (0-50%)
12. customsolvent evaporated in vacuo
13. customThe resulting crude product was purified further by Mass Directed Autopreparation