反应详情

To a solution of 9-BBN in THF (24 ml, 12 mmol, 0.5 M) was added 2-methyl-3-buten-2-ol (345 mg, 4.0 mmol) and the resulting solution was stirred under N2 at rt for overnight. In a second flask charged with PdCl2(dppf) (324 mg, 0.40 mmol), Cs2CO3 (2.4 g, 8.0 mmol) and Ph3As (124 mg, 0.4 mmol) was added 2-(6-bromo-9-chloro-1H-phenanthro[9,10-d]imidazol-2-yl)isophthalonitrile from Example 36, DMF (24 ml) and H2O (0.88 ml) and the mixture was stirred under N2 for 5 minutes. The hydroboration mixture was then transferred to the second flask and the resulting reaction suspension was stirred at rt under N2 for 5 days. After being treated with brine, the aqueous phase was extracted with EtOAc and the combined organic solution was washed with water and brine, dried over MgSO4. After removing the drying agent by filtration, the solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (50% EtOAc/Hexane) to yield 600 mg of 2-[9-chloro-6-(3-hydroxy-3-methylbutyl)-1H-phenanthro[9,10-d]imidazol-2-yl)isophthalonitrile as a yellow solid. 1H NMR (400 MHz, Acetone): δ 13.10 (s br, 1H); 8.94 (s, 1H); 8.77 (s, 1H); 8.70-8.60 (m br, 2H); 8.39 (d, 2H); 8.03 (t, 1H); 7.75 (dd, 1H); 7.69 (dd, 1H); 4.92 (s, 1H); 3.05 (m, 2H); 1.95 (m, 2H); 1.33 (s, 6H).

1. stirringthe mixture was stirred under N2 for 5 minutes
2. customthe resulting reaction suspension
3. stirringwas stirred at rt under N2 for 5 days
4. extractionthe aqueous phase was extracted with EtOAc
5. washthe combined organic solution was washed with water and brine
6. dry with materialdried over MgSO4
7. customAfter removing the drying agent
8. filtrationby filtration
9. concentrationthe solution was concentrated under reduced pressure
10. customthe residue was purified by silica gel chromatography (50% EtOAc/Hexane)