反应详情

To a degassed solution of 4-[(4-Iodophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol (144) (0.305 g, 0.68 mmol) in DMF (8 mL) were added Pd(PPh3)2Cl2 (48 mg, 0.07 mmol), CuI (13 mg, 0.07 mmol), N,N-diisopropylethylamine (0.55 mL, 3.10 mmol) and trimethylsilyl acetylene (0.12 mL, 0.82 mmol). The reaction mixture was stirred at room temperature overnight, poured into saturated aqueous NH4Cl (20 mL) and water (10 mL), extracted with EtOAc (2×50 mL). The combined organic phase washed with water, brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as dark brown oil. The crude product was purified by chromatography on a silica gel column eluted with a gradient from hexanes to 15% EtOAc:hexanes to give light brown solid, which washed with cold hexanes to yield 0.18 g (64%) of the title compound 146 as an off-white solid. 1H NMR (400 MHz, CDCl3): δ 0.22 (s, 9H), 0.89 (s, 6H), 0.92 (s, 6H), 1.27 (s, 2H), 1.91 (s, 2H), 1.97 (s, 2H), 4.55 (br s, 1H), 6.72 (d, J=8.5 Hz, 2H), 7.00 (d, J=8.4 Hz, 2H), 7.08 (d, J=8.2 Hz, 2H), 7.36 (d, J=8.3 Hz, 2H). LCMS (ESI): m/z 415 (M−H)−.

1. extractionextracted with EtOAc (2×50 mL)
2. washThe combined organic phase washed with water, brine
3. dry with materialdried over Na2SO4
4. filtrationfiltered
5. concentrationthe filtrate was concentrated
6. customto give the crude product as dark brown oil
7. customThe crude product was purified by chromatography on a silica gel column
8. washeluted with a gradient from hexanes to 15% EtOAc
9. customhexanes to give light brown solid, which
10. washwashed with cold hexanes