Palladium-Catalyzed Desulfitative Mizoroki-Heck Coupling Reactions of Sulfonyl Chlorides with Olefins in a Nitrile-Functionalized Ionic Liquid

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. [C₃CNpy][Tf₂N]. 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

References and Notes

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Dubbaka, S. R.; Vogel, P.; submitted.

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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), K₂CO₃ (1.5 equiv, 2.25 mmol), Me(Oct)₃NCl (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 Et₂O (3 × 15 mL). The combined extracts were washed with brine and H₂O and then dried with Na₂SO₄. 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 Et₂O and placed under vacuum for 18 h prior to the next catalytic cycle.