Ru/C-Catalyzed Carbonylation at ortho-C-H Bonds in 2-Phenylpyridines

Shinya Imoto; Takeshi Uemura; Fumitoshi Kakiuchi; Naoto Chatani

doi:10.1055/s-2006-958451

LETTER

Ru/C-Catalyzed Carbonylation at ortho-C-H Bonds in 2-Phenylpyridines

Shinya Imoto^a, Takeshi Uemura^a, Fumitoshi Kakiuchi^b, Naoto Chatani*^a
^a Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
Fax: +81(6)68797396; e-Mail: chatani@chem.eng.osaka-u.ac.jp;
^b Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan

Abstract

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Abstract

Ru/C also exhibits catalytic activity for carbonylation at ortho-C-H bonds in 2-phenylpyridines.

Key words

acylations - carbonylations - catalysis - heterocycles - ruthenium

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References

References and Notes

<A NAME="RU11106ST-1">1</A> For a recent review, see: Kakiuchi F. Chatani N. Adv. Synth. Catal. 2003, 345: 1077

<A NAME="RU11106ST-2A">2a</A> Chatani N. Fukuyama T. Kakiuchi F. Murai S. J. Am. Chem. Soc. 1996, 118: 493

<A NAME="RU11106ST-2B">2b</A> Chatani N. Fukuyama T. Tatamidani H. Kakiuchi F. Murai S. J. Org. Chem. 2000, 65: 4039

<A NAME="RU11106ST-3">3</A> Fukuyama T. Chatani N. Tatsumi J. Kakiuchi F. Murai S. J. Am. Chem. Soc. 1998, 120: 11522

<A NAME="RU11106ST-4A">4a</A> Chatani N. Ie Y. Kakiuchi F. Murai S. J. Org. Chem. 1997, 62: 2604

<A NAME="RU11106ST-4B">4b</A> Fukuyama T. Chatani N. Kakiuchi F. Murai S. J. Org. Chem. 1997, 62: 5647

<A NAME="RU11106ST-4C">4c</A> Ie Y. Chatani N. Ogo T. Marshall DR. Fukuyama T. Kakiuchi F. Murai S. J. Org. Chem. 2000, 65: 1475

<A NAME="RU11106ST-4D">4d</A> Asaumi T. Chatani N. Matsuo T. Kakiuchi F. Murai S. J. Org. Chem. 2003, 68: 7538

<A NAME="RU11106ST-4E">4e</A> Asaumi T. Matsuo T. Fukuyama T. Ie Y. Kakiuchi F. Chatani N. J. Org. Chem. 2004, 69: 4433

<A NAME="RU11106ST-4F">4f</A> Chatani N. Uemura T. Asaumi T. Ie Y. Kakiuchi F. Murai S. Can. J. Chem. 2005, 83: 755

<A NAME="RU11106ST-5">5</A> Chatani N. Yorimitsu S. Asaumi T. Kakiuchi F. Murai S. J. Org. Chem. 2002, 67: 7557

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Recent reviews on Pd/C, see:

<A NAME="RU11106ST-7A">7a</A> Blaser H.-U. Indolese A. Schnyder A. Steiner H. Studer M. J. Mol. Catal. A: Chem. 2001, 173: 3

<A NAME="RU11106ST-7B">7b</A> Biffis A. Zecca M. Basato M. J. Mol. Catal. A: Chem. 2001, 173: 249

<A NAME="RU11106ST-7C">7c</A> Felpin F.-X. Ayad T. Mitra S. Eur. J. Org. Chem. 2006, 2679

<A NAME="RU11106ST-8">8</A> For a paper on Ru/C-catalyzed reaction, see: Murahashi S. Naota T. Kuwabara T. Saito T. Kumobayashi H. Akutagawa S. J. Am. Chem. Soc. 1990, 112: 782

General Procedure for the Ru/C-Catalyzed Reactions of 2-Arylpyridines with Ethylene and CO.
In a 50-mL stainless-steel autoclave were placed 5 wt% Ru/C (101 mg, corresponding to 0.05 mmol of Ru atom), 2-phenylpyridine (1a, 310 mg, 2 mmol), and DMA (6 mL). After flushing the system with 10 atm of ethylene three times, it was pressurized with ethylene to 7 atm and then with CO to an additional 20 atm. The autoclave was then immersed in an oil bath at 160 °C. After 20 h had elapsed, it was removed from the oil bath, allowed to cool and the gases were then released. The contents were transferred to a round-bottomed flask with EtOAc. After evaporation, the resulting residue was subjected to column chromatography on silica gel with hexane-EtOAc as the eluent to give 1-{2-[2-(pyridinyl)phenyl]}-1-propanone (2a, 346 mg, 81% yield) and 1-[2-(3-propionyl-2-pyridinyl)phenyl]-1-propanone (3a, 6 mg, 1% yield).