Palladium Nanoparticles in Polymers: Catalyst for Alkene Hydrogenation, Carbon-Carbon Cross-Coupling Reactions, and Aerobic Alcohol Oxidation

Abstract

A new recyclable palladium catalyst was synthesized by a simple procedure from readily available reagents, which is composed of palladium nanoparticles dispersed in an organic polymer. This catalyst is robust, and highly active in many organic transformations including alkene and alkyne hydrogenation, carbon-carbon cross-coupling reactions, and aerobic alcohol oxidation.

Key words

palladium - heterogeneous - hydrogenation - oxidations - cross-coupling - polymer

References

• 1 Negishi E.-I. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley; New York: 2002. 
• 2a Lysén M. Köhler K. Synthesis  2006,  692 
• 2b Shokouhimehr M. Kim J.-H. Lee Y.-S. Synlett  2006,  618 
• 2c He HS. Yan JJ. Shen R. Zhuo S. Toy PH. Synlett  2006,  563 
• 2d Uozumi Y. Kikuchi M. Synlett  2005,  1775 
• 2e Crudden CM. Sateesh M. Lewis R. J. Am. Chem. Soc.  2005,  127:  10045 
• 2f Wang Y. Sauer DR. Org. Lett.  2005,  6:  2793 
• 2g Motokura K. Fujita N. Mori K. Mizugaki T. Ebitani K. Kaneda K. Tetrahedron Lett.  2005,  46:  5507 
• 2h Yamada YMA. Takeda K. Takahashi H. Ikegami S. Tetrahedron  2004,  60:  4097 
• 2i Ramesh C. Nakamura R. Kubota Y. Miwa M. Sugi Y. Synthesis  2003,  501 
• 3a Koutsopoulos S. Johannessen T. Eriksen KM. Fehrmann R. J. Catal.  2006,  238:  206 
• 3b Silvestre-Albero J. Rupprechter G. Freund H. Chem. Commun.  2006,  80 
• 3c Narayanan R. El-Sayed MA. J. Catal.  2005,  234:  348 
• 3d Son HK. Jang Y. Park J. Na HB. Park HM. Yun HJ. Lee J. Hyeon T. J. Am. Chem. Soc.  2004,  126:  5026 
• 3e Bhanage BM. Fujita S. Yoshida T. Sano Y. Arai M. Tetrahedron Lett.  2003,  44:  3505 
• 3f Kim SW. Kim M. Lee WY. Hyeon T. J. Am. Chem. Soc.  2002,  124:  5990 
• 3g Reetz MT. Westermann E. Angew. Chem. Int. Ed.  2000,  39:  165 
• 3h Reetz MT. Breinbauer R. Wanninger K. Tetrahedron Lett.  1996,  37:  4499 
• 4a Chung M.-K. Schlaf M. J. Am. Chem. Soc.  2004,  126:  7386 
• 4b Roucoux A. Schulz J. Patin H. Chem. Rev.  2002,  102:  3757 
• 4c Schmid G. Chi LF. Adv. Mater.  1998,  10:  515 
• 5a Hagio H. Sugiura M. Kobayashi S. Org. Lett.  2006,  8:  375 
• 5b Nishio R. Sugiura M. Kobayashi S. Org. Lett.  2005,  7:  483 
• 5c Okamoto K. Akiyama R. Yoshida H. Yoshida T. Kobayashi S. J. Am. Chem. Soc.  2005,  127:  2125 
• 5d Okamoto K. Akiyama R. Kobayashi S. Org. Lett.  2004,  6:  1987 
• 5e Okamoto K. Akiyama R. Kobayashi S. J. Org. Chem.  2004,  69:  2871 
• 5f Akiyama R. Kobayashi S. J. Am. Chem. Soc.  2003,  125:  3412 
• 6a Kim W.-H. Park IS. Park J. Org. Lett.  2006,  8:  2543 
• 6b Kwon MS. Kim N. Seo SH. Park IS. Cheedrala RK. Park J. Angew. Chem. Int. Ed.  2005,  44:  6913 
• 6c Kwon MS. Kim N. Park CM. Lee JS. Kang KY. Park J. Org. Lett.  2005,  7:  1077 
• 6d Park IS. Kwon MS. Kim N. Lee JS. Kang KY. Park J. Chem. Commun.  2005,  5667 
• 6e Kim N. Kwon MS. Park CM. Park J. Tetrahedron Lett.  2004,  45:  7057 
• 8a Chauhan BS. Rathore J. Bandoo T. J. Am. Chem. Soc.  2004,  126:  8493 
• 8b Pillai UR. Sahle-Demessie E. J. Mol. Catal. A: Chem.  2004,  222:  153 
• 8c Yoon B. Kim H. Wai CM. Chem. Commun.  2003,  1040 
• 8d Berthold H. Schotten T. Honig H. Synthesis  2002,  1607 

7

Pd nanoparticles were generated from Pd(PPh₃)₄ in a mixture of butan-1-ol and THF before the polymerization with AIBN.

9

Ph₃PO was recovered from the filtrate in more than 90% yield.

10

In the cases of butan-2-ol and tetra(ethylene glycol), the resulting catalysts showed 26% of the activity of 1 and 44%, respectively.

11

In the combinations of methacrylic acid and ethylene glycol dimethacrylate, methyl acrylate and ethylene glycol dimethacrylate, and acrylamide and 2,3-dimethylbuta-1,3-diene, the resulting catalysts showed 22% of the activity of 1, 34%, 3%, respectively.

12

In the filtrate, neither Ph₃P nor Ph₃PO were detected by ¹H NMR spectroscopy, and Pd was not detected by ICP analysis.

13

The filtrate was clear and colorless. Thus, the Pd content in the catalyst was estimated by assuming that all the Pd in the Pd(PPh₃)₄ was entrapped in the catalyst.