Cesium fluoride → HCID 136216273, compound

Participants

Reaction Conditions

Reaction Steps

To a degassed mixture of 4-(2-bromo-4-chloro-phenyl)-1-methyl-3-(2-pyridyl)-4,6,7,8-tetrahydropyrazolo[3,4-e][1,4]thiazepine (0.50 g, 1.2 mmol, Example #D.37) and tributyl(vinyl)stannane (0.37 mL, 1.3 mmol) in DMF (5 mL) was added cesium fluoride (0.35 g, 2.3 mmol), copper(I) iodide (0.022 g, 0.12 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.066 g, 0.058 mmol). The resulting mixture was heated at about 45° C. overnight; then diluted with DCM (50 mL), washed with water (20 mL) and brine (20 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate/hexanes 1:1) to give 4-(4-chloro-2-vinyl-phenyl)-1-methyl-3-(2-pyridyl)-4,6,7,8-tetrahydropyrazolo[3,4-e][1,4]thiazepine (0.28 g, 0.73 mmol, 63%) as an off white solid: LC-MS (Table 1, Method a) Rt=4.07 min; m/z 383 (M+H)+; 1H-NMR (CDCl3, Bruker 400 MHz) 2.69-2.78 (1 H, m) 2.81-2.89 (1 H, m) 3.19-3.28 (1 H, m) 3.52-3.61 (1 H, m) 3.77-3.86 (1 H, m) 3.84 (3 H, s) 5.47 (1 H, dd, J=11.0, 1.5 Hz) 5.73 (1 H, dd, J=17.5, 1.5 Hz) 6.79 (1 H, s) 7.02-7.08 (2 H, m) 7.14 (1 H, d, J=8.5 Hz) 7.38 (1 H, dd, J=17.5, 11.0 Hz) 7.45 (1 H, d, J=2.0 Hz) 7.58 (1 H, td, J=7.5, 2.0 Hz) 7.77 (1 H, br.d, J=8.0 Hz) 8.42 (1 H, br.d, J=5.0 Hz).

Provenance & Evidence