Heck Reaction in Water with Amphiphilic Resin-Supported Palladium-Phosphine Complexes

Abstract

The Heck reaction of various aryl halides and alkenes took place in water in the presence of an amphiphilic polystyrene-poly(ethylene glycol) resin-supported palladium-phosphine complex to give the corresponding styrene derivatives in quantitative yields.

Key words

Heck reaction - palladium catalysis in water - amphi­philic polymer-supported catalysts

References

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1

Visiting graduate student from Gifu University.

7

One isolated example of a water-based Heck reaction using an amphiphilic resin-supported palladium catalyst was reported in ref. 5c.

8

Loading of Pd (mmol/g) of the supported catalysts: 4: 0.32, 5: 0.32, 6: 0.33, 7: 0.61, 8: 0.55, 9: 0.32, 10: 0.33, 11: 0.52.

11

Purchased from Argonaut Technologies, San Carlos, CA, USA.

13

A typical procedure is given for the reaction of iodobenzene (1a) and acrylic acid (2) (Table [2] , entry 1). A Merrifield vessel was charged with potassium hydroxide (168 mg, 3 mmol), 4 (313 mg, 0.1 mmol Pd) and 2.5 mL of water. To the mixture was added iodobenzene (1a) (204 mg, 1.0 mmol) and acrylic acid (2) (144 mg, 2.0 mmol) at 25 °C and the reaction mixture was shaken on a wrist-action shaker for 14 h. The reaction mixture was filtered and the resin was extracted and rinsed with an aqueous solution of NaHCO₃
(3 ¥ 2 mL). The combined aqueous phase was acidified by hydrochloric acid (pH ≅ 1) and extracted with diethyl ether (3 × 10 mL). The extract was dried over Na₂SO₄ and concentrated under reduced pressure to give a quantitative yield of 3a (93% purity on GC analysis). The product was filtered through silica gel pad (eluent: hexane/EtOAc = 10/1) to give 142 mg (96%) of the analytically pure cinnamic acid (3a) as a white powder.

14

A toluene solution of anisyl iodide (1e) (mp 53 °C) was added to disperse smoothly to the aqueous reaction mixture.