Abstract
Aryl and alkenyl sulfonyl chlorides can be used in Heck-Mizoroki-type couplings with mono- and disubstituted olefins in a nitrile-functionalized ionic liquid, viz. [C3 CNpy][Tf2 N]. Advantages over previously reported methods include: (1) use of a cheap catalyst source, PdCl2 , (2) ability to handle the catalyst in air, (3) reduced reaction times, (4) elimination of phase-transfer catalysts due to the high solubility of the inorganic base in the ionic liquid, and (5) facile recycling of the ionic liquid-palladium catalyst. The yields of coupling products remain in the same range as the reactions conducted in organic solvents. Palladium nanoparticles, characterized using transmission electron microscopy, have been identified in the ionic liquid following the Heck-Mizoroki type coupling reactions.
Key words
Mizoroki-Heck reaction - ionic liquids - palladium - sulfonyl chlorides - nanoparticles
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General Procedure for Desulfitative Palladium-Catalyzed Mizoroki-Heck Reaction of Sulfonyl Chlorides with Monosubstituted Olefins
To a Schlenk tube, the sulfonyl chloride (1 equiv, 1.5 mmol), PdCl2 (1 mol%, 0.015 mmol), K2 CO3 (1.5 equiv, 2.25 mmol), Me(Oct)3 NCl (15 mol%, 0.23 mmol) and IL 1 (2 mL) were added. After the mixture was flushed with nitrogen, the olefin (2.0 equiv, 3.0 mmol) was added. The reaction mixture was heated at 140 °C for 1-2 h. After cooling to r.t., the product was extracted with Et2 O (3 × 15 mL). The combined extracts were washed with brine and H2 O and then dried with Na2 SO4 . The coupling product was obtained after removal of solvent. An external standard (diphenylmethane, 0.6 mmol) was used for GC analysis. The ionic liquid phase was washed with Et2 O and placed under vacuum for 18 h prior to the next catalytic cycle.
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