反应详情

A 250 mL three-neck flask equipped with a reflux condenser and nitrogen inlet was charged with benzyl 4,5,6-trichloropicolinate (17.77 g, 56.10 mmol), 2-(4-chloro-2-fluoro-3-methoxyphenyl)-1,3,2-dioxaborinane (19.20 g, 79.0 mmol) and CsF (17.04 g, 112.0 mmol). Acetonitrile (100 mL) and water (30 mL) were added. The reaction mixture was evacuated/backfilled with nitrogen (5×). Solid Pd(PPh3)2Cl2 (1.724 g, 2.456 mmol) was added. The solution was evacuated/backfilled with nitrogen (5×) and then stirred at reflux for 90 min. A white solid precipitated upon cooling to room temperature. The solid was filtered, washed with water and dried in air (18.66 g, 75%): 1H NMR (400 MHz, CDCl3) δ 8.23 (s, 1H, pyridine H), 7.52-7.32 (m, 5H, phenyl), 7.27 (dd, JH-H=8.4 Hz, JF-H=1.7 Hz, 1H, aromatic), 7.10 (dd, JH-H=8.4 Hz, JF-H=6.8 Hz, 1H, aromatic), 5.44 (s, 2H, CH2Ph), 3.98 (d, J JF-H=1.3 Hz, 3H, OMe); 13C{1H} NMR (101 MHz, CDCl3) δ 163.0, 153.7, 153.5 (d, JF-C=253 Hz, C2′), 146.0, 144.5 (d, JF-C=13 Hz), 144.1, 135.0, 134.2, 129.9 (d, JF-C=3 Hz), 128.5, 126.1, 125.8 (d, JF-C=14 Hz), 125.3 (d, JF-C=3 Hz), 124.9 (d, JF-C=2 Hz), 67.9 (CH2), 61.5 (d, JF-C=4 Hz, OMe). Anal. Calcd for C20H13Cl3FNO3: C, 54.51; H, 2.97; N, 3.18. Found: C, 54.60; H, 3.08; N, 3.16.

1. customA 250 mL three-neck flask equipped with a reflux condenser and nitrogen inlet
2. temperatureat reflux for 90 min
3. customA white solid precipitated
4. filtrationThe solid was filtered
5. washwashed with water
6. customdried in air (18.66 g, 75%)