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.

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

References

1

Visiting graduate student from Gifu University.

For reviews, see:

2a Li C.-J. Chan T.-H. Organic Reactions in Aqueous Media   Wiley-VCH; New York: 1997. 

2b Grieco PA. Organic Synthesis in Water   Kluwer Academic Publishers; Dordrecht: 1997. 

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3c Burgess K. Porte AM. Adv. Catal. Proc.  1997,  2:  69 

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3e Dörwald FZ. Organic Synthesis on Solid Phase   Wiley-VCH; Weinheim: 2000. 

4 Uozumi Y. Hayashi T. Solid-Phase Palladium Catalysis for High-throughput Organic Synthesis, In Handbook of Combinatorial Chemistry   Nicolaou KC. Hanko R. Hartwig W. Wiley-VCH; Weinheim: 2002.  p.531-584  

5a Uozumi Y. Danjo H. Hayashi T. Tetrahedron Lett.  1997,  38:  3557 

5b Uozumi Y. Danjo H. Hayashi T. J. Org. Chem.  1999,  64:  3384 

5c Uozumi Y. Watanabe T. J. Org. Chem.  1999,  64:  6921 

5d Danjo H. Tanaka D. Hayashi T. Uozumi Y. Tetrahedron  1999,  55:  14341 

5e Uozumi Y. Nakazono M. Adv. Synth. Catal.  2002,  344:  274 

5f

Uozumi, Y.; Kobayashi, Y. Heterocycles 2003, in press.

For recent examples of the Heck reaction in water, see:

6a Amengual R. Genin E. Michelet V. Savignac M. Genet J.-P. Adv. Synth. Catal.  2002,  344:  393 

6b Mukhopadyay S. Rothenberg G. Joshi A. Baidossi M. Sasson Y. Adv. Synth. Catal.  2002,  344:  348 

6c Genet J.-P. Savignac M. J. Organomet. Chem.  1999,  576:  305 ; and references cited therein

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.

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10 PEGA resin is a copolymerisate of acrylamidopropyl(2-aminopropyl)polyethylene glycol and N,N-dimethylacryl-amide crosslinked with bis(2-acrylamidopropyl)poly-ethylene glycol, see: Meldal M. Tetrahedron Lett.  1992,  33:  3077 

11

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

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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.

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16 For a review of the asymmetric Heck reaction, see: Shibasaki M. Vogl EM. In Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin, Heidelberg: 1999.  p.457-487  

For recent examples of asymmetric palladium catalysis in water using PS-PEG resin-supported chiral catalysts, see:

17a Uozumi Y. Danjo H. Hayashi T. Tetrahedron Lett.  1998,  39:  8303 

17b Uozumi Y. Shibatomi K. J. Am. Chem. Soc.  2001,  123:  2919