反应详情

Aqueous Na2CO3 (1.4 mL, 2.0 M) was added to the ethyl (trifluoro-methane-sulfonyloxy)cinnamate (0.55 g, 1.53 mmol), 3-(1-adamantyl)-4-benzyloxyphenylboronic acid (0.50 g, 1.38 mmol) [1H NMR spectrum (300 MHz, CDCl3) δ 1.77, 2.26 (2 s, 12, AdCH2), 2.07 (s, 3, AdCH), 5.21 (s, 2, CH2), 7.06 (d, J=8.2 Hz, 1, ArH), 7.3–7.5 (mn, 5, ArH), 8.03 (d, J=7.8 Hz, 1, ArH), 8.19 ppm (s, 1, ArH)], tetrakis(triphenylphosphine)palladium (0.16 g, 0.14 mmol), and lithium chloride (0.13 g, 3.1 mmol) in dimethoxyethane (12 mL) under argon. The mixture was heated at reflux (80–85° C.) overnight to achieve the biaryl coupling, then worked-up, and chromatographed (10% ethyl acetate/hexane) to give ethyl (E)-4-[3-(1-adamantyl)-4-benzyloxyphenyl]-3-chlorocinnamate as a white solid (0.58 g, 79%): m.p. 148–150° C.; Rf0.61 (20% ethyl acetate/hexane); 1H NMR spectrum (300 MHz, CDCl3) δ 1.73, 2.17 (2 s, 12, AdCH2), 2.04 (s, 3, AdCH), 1.33 (t, J=7.1 Hz, 3 CH3), 4.26 (q, J=7.1 Hz, 2, CH2), 5.17 (s, 2, CH2), 6.46 (d, J=15.9 Hz, 1, HC═CCO), 7.00 (d, J=8.2 Hz, 1, ArH), 7.3–7.5 (m, 8, ArH), 7.52 (d, J=7.1 Hz, 1, ArH), 7.62 (s, 1, ArH), 7.65 ppm (d, J=15.4 Hz, 1, C═CHCO).

1. temperatureThe mixture was heated
2. temperatureat reflux (80–85° C.) overnight
3. customchromatographed (10% ethyl acetate/hexane)