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Synthesis 2009(16): 2674-2678  
DOI: 10.1055/s-0029-1216895
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Bimetallic Palladium-Platinum-on-Carbon-Catalyzed H-D Exchange Reaction: Synergistic Effect on Multiple Deuterium Incorporation

Tomohiro Maegawaa,1, Nobuhiro Itob, Keiji Oonob, Yasunari Monguchia, Hironao Sajiki*a
a Laboratory of Organic Chemistry, Department of Organic and Medicinal Chemistry, Gifu Pharmaceutical University, Gifu 502-8585, Japan
b Chemical Products Research Laboratories, Wako Pure Chemical Industries, Ltd., Matoba, Kawagoe 350-1101, Japan
Fax: +81(58)2375979; e-Mail: sajiki@gifu-pu.ac.jp;
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Publikationsverlauf

Received 12 February 2009
Publikationsdatum:
10. Juli 2009 (online)

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Abstract

We prepared several activated carbon-supported bimetallic Pd-Pt catalysts (Pd-Pt/C) by using various reducing reagents, and examined their catalytic activities for the deuteration of alkyl-substituted aromatic compounds. Multiple deuterations catalyzed by Pt-Pd/C proceeded in D2O at 180 ˚C under a H2 atmosphere, and a synergistic effect was observed in relation to the incorporation of deuterium at sterically hindered positions on aromatic rings.

Key words

heterogeneous catalysis - palladium - platinum - H-D exchange - synergy - bimetallic

    References

  • 2a Atzrodt J. Derdau V. Fey T. Zimmermann J. Angew. Chem. Int. Ed.  2007,  46:  7744 
    Suche in Google Scholar
  • 2b Junk T. Catallo WJ. Chem. Soc. Rev.  1997,  26:  401 
    Suche in Google Scholar
  • 3a Brown WG. Garnett JL. J. Am. Chem. Soc.  1958,  80:  5272 
    Suche in Google Scholar
  • 3b Fraser RR. Renaud RN. J. Am. Chem. Soc.  1966,  88:  4365 
    Suche in Google Scholar
  • 3c Garnett JL. Hodges RJ. J. Am. Chem. Soc.  1967,  89:  4546 
    Suche in Google Scholar
  • 3d Garnett JL. Long MA. McLaren AB. Peterson KB. J. Chem. Soc., Chem. Commun.  1973,  749 
  • 3e Blake MR. Garnett JL. Gregor IK. Hannan W. Hoa K. Long MA. J. Chem. Soc., Chem. Commun.  1975,  930 
  • 3f Hesk D. Jones JR. Lockley WJS. J. Labelled Compd. Radiopharm.  1990,  28:  1427 
    Suche in Google Scholar
  • 3g Hesk D. Jones JR. Lockley WJS. J. Pharm. Sci.  1991,  80:  887 
    Suche in Google Scholar
  • 3h Heys JR. Shu AYL. Senderoff SG. Phillips NM. J. Labelled Compd. Radiopharm.  1993,  33:  431 
    Suche in Google Scholar
  • 3i Lukey CA. Long MA. Garnett JL. Aust. J. Chem.  1995,  48:  79 
    Suche in Google Scholar
  • 3j Buncel E. Clement O. J. Chem. Soc., Perkin Trans. 2  1995,  1333 
  • 3k Van Genderen MHP. Pfaadt M. Moller C. Valiyaveettil S. Spiess HW. J. Am. Chem. Soc.  1996,  118:  3661 
    Suche in Google Scholar
  • 3l Hardacre C. Holbrey JD. McMath SEJ. Chem. Commun.  2001,  367 
  • 3m Klei SR. Golden JT. Tilley TD. Bergman RG. J. Am. Chem. Soc.  2002,  124:  2092 
    Suche in Google Scholar
  • 3n Hickey MJ. Jones JR. Kingston LP. Lockley WJS. Mather AN. McAuley BM. Wilkinson DJ. Tetrahedron Lett.  2003,  44:  3959 
    Suche in Google Scholar
  • 3o Matsubara S. Yokota K. Oshima K. Chem. Lett.  2004,  33:  294 
    Suche in Google Scholar
  • 3p Yamamoto M. Oshima K. Matsubara S. Chem. Commun.  2004,  1714 
  • 3q Yamamoto M. Oshima K. Matsubara S. Org. Lett.  2004,  6:  5015 
    Suche in Google Scholar
  • 3r Takahashi M. Oshima K. Matsubara S. Chem Lett.  2005,  34:  192 
    Suche in Google Scholar
  • 3s Ishibashi K. Takahashi M. Yokota Y. Oshima K. Matsubara S. Chem Lett.  2005,  34:  664 
    Suche in Google Scholar
  • 3t Derdau V. Atzrodt J. Synlett  2006,  1918 
  • 3u Yamamoto M. Oshima K. Matsubara S. Heterocycles  2006,  67:  353 
    Suche in Google Scholar
  • 3v Prechtl MHG. Holscher M. Ben-David Y. Theyssen N. Loschen R. Milstein D. Leitner W. Angew. Chem. Int. Ed.  2007,  46:  2269 
    Suche in Google Scholar
  • 4a Junk T. Catallo WJ. Tetrahedron Lett.  1996,  37:  3445 
    Suche in Google Scholar
  • 4b Junk T. Catallo WJ. Civils LD. J. Labelled Compd. Radiopharm.  1997,  36:  625 
    Suche in Google Scholar
  • 4c Junk T. Catallo WJ. Elguero J. Tetrahedron Lett.  1997,  38:  6309 
    Suche in Google Scholar
  • 5a Vaidyanathan S. Surber BW. Tetrahedron Lett.  2005,  46:  5195 
    Suche in Google Scholar
  • 5b Hakala U. Wahala K. J. Org. Chem.  2007,  72:  5817 
    Suche in Google Scholar
  • 6a Garnett JL. Hodges RJ. J. Am. Chem. Soc.  1967,  89:  4645 
    Suche in Google Scholar
  • 6b Garnett JL. Hodges RJ. Chem. Commun.  1967,  1001 
  • 6c Bean GP. Johnson AR. Katritzky AR. Ridgewell BJ. White AM. J. Chem. Soc. B  1967,  1219 
  • 6d Long MA. Garnett JL. Vining RFW. Mole T. J. Am. Chem. Soc.  1972,  94:  8632 
    Suche in Google Scholar
  • 6e Werstiuk NH. Kadai T. Can. J. Chem.  1974,  52:  2169 
    Suche in Google Scholar
  • 6f Tashiro M. Nakayama K. J. Chem. Soc., Perkin Trans. 1  1983,  2315 
  • 6g Iranzo GY. Elguero J. J. Labelled Compd. Radiopharm.  1990,  28:  967 
    Suche in Google Scholar
  • 6h Okazaki M. Uchino N. Nozaki N. Kubo K. Bull. Chem. Soc. Jpn.  1995,  68:  1024 
    Suche in Google Scholar
  • 7a Sajiki H. Hattori K. Aoki F. Yasunaga K. Hirota K. Synlett  2002,  1149 
  • 7b Sajiki H. Aoki F. Esaki H. Maegawa T. Hirota K. Org. Lett.  2004,  6:  1485 
    Suche in Google Scholar
  • 7c Sajiki H. Kurita T. Esaki H. Aoki F. Maegawa T. Hirota K. Org. Lett.  2004,  6:  3521 
    Suche in Google Scholar
  • 7d Maegawa T. Akashi A. Esaki H. Aoki F. Sajiki H. Hirota K. Synlett  2005,  845 
  • 7e Sajiki H. Esaki H. Aoki F. Maegawa T. Hirota K. Synlett  2005,  1385 
  • 7f Maegawa T. Akashi A. Esaki H. Aoki F. Sajiki H. Hirota K. Synlett  2005,  845 
  • 7g Sajiki H. Ito N. Esaki H. Maesawa T. Maegawa T. Hirota K. Tetrahedron Lett.  2005,  46:  6995 
    Suche in Google Scholar
  • 7h Esaki H. Aoki F. Maegawa T. Hirota K. Sajiki H. Heterocycles  2005,  66:  361 
    Suche in Google Scholar
  • 7i Esaki H. Ito N. Sakai S. Maegawa T. Monguchi Y. Sajiki H. Tetrahedron  2006,  62:  10954 
    Suche in Google Scholar
  • 7j Esaki H. Ohtaki R. Maegawa T. Monguchi Y. Sajiki H. J. Org. Chem.  2007,  72:  2143 
    Suche in Google Scholar
  • 7k Esaki H. Aoki F. Umemura M. Kato M. Maegawa T. Monguchi Y. Sajiki H. Chem. Eur. J.  2007,  13:  4052 
    Suche in Google Scholar
  • 7l Ito N. Esaki H. Maesawa T. Imamiya E. Maegawa T. Sajiki H. Bull. Chem. Soc. Jpn.  2008,  81:  278 
    Suche in Google Scholar
  • 7m Kurita T. Hattori K. Seki S. Mizumoto T. Aoki F. Yamada Y. Ikawa K. Maegawa T. Monguchi Y. Sajiki H. Chem. Eur. J.  2008,  14:  664 
    Suche in Google Scholar
  • 7n Kurita T. Aoki F. Mizumoto T. Maejima T. Esaki H. Maegawa T. Monguchi Y. Sajiki H. Chem. Eur. J.  2008,  14:  3371 
    Suche in Google Scholar
  • 8 Maegawa T. Fujiwara Y. Inagaki Y. Esaki H. Monguchi Y. Sajiki H. Angew. Chem. Int. Ed.  2008,  47:  5394 
    CrossrefPubMedSuche in Google Scholar
  • 9 Maegawa T. Fujiwara Y. Inagaki Y. Monguchi Y. Sajiki H. Adv. Synth. Catal.  2008,  350:  2215 
    CrossrefSuche in Google Scholar
  • 10a Ito N. Watahiki T. Maesawa T. Maegawa T. Sajiki H. Adv. Synth. Catal.  2006,  348:  1025 
    Suche in Google Scholar
  • 10b Ito N. Watahiki T. Maesawa T. Maegawa T. Sajiki H. Synthesis  2008,  1467 
  • 11a Mozingo R. Org. Synth. Coll. Vol. III   John Wiley & Sons; London: 1955.  p.685 
  • 11b Alexander ER. Cope AC. J. Am. Chem. Soc.  1944,  66:  886 
    Suche in Google Scholar
  • 11c Arimoto O, and Katayama S. inventors; JP  7090664.  Chem. Abstr. 1995, 122, 324895
  • 11d Scott RWJ. Datye AK. Crooks RM. J. Am. Chem. Soc.  2003,  125:  3708 
    Suche in Google Scholar
  • 11e Crooks RM. Zhao M. Sun L. Chechik V. Yeung LK. Acc. Chem. Res.  2001,  34:  181 
    Suche in Google Scholar
  • 13a Koutsopoulos S. Eriksen KM. Fehrman R. J. Catal.  2006,  238:  270 
    Suche in Google Scholar
  • 13b Matsui T. Harada M. Bnado KK. Toba M. Yoshimura Y. Appl. Catal., A  2005,  290:  73 
    Suche in Google Scholar
  • 13c Navarro RM. Pawelec B. Trejo JM. Mariscal R. Fierro JLG. J. Catal.  2000,  189:  184 
    Suche in Google Scholar
  • 13d Fujikawa T. Tsuji K. Mizuguchi H. Goto H. Idei K. Usui K. Catal. Lett.  1999,  63:  27 
    Suche in Google Scholar
  • 13e Karpiński Z. Kościelski T. J. Catal.  1980,  63:  313 
    Suche in Google Scholar
1

Present address: Graduate School of Pharmaceutical Sciences, Osaka University, Suita Osaka, 565-0871, Japan.

12

The Pt and Pd contents of 5% Pd-Pt/C(NaBH4) were almost equal (Pd, 3.6%; Pt, 3.5% by ICP-AES), whereas 5% Pd-Pt/C(H2), 5% Pd-Pt/C(NH2NH2), and 5% Pd-Pt/C(HCHO) showed higher contents of Pd than of Pd (Pd, 3.9-4.1%; Pt, 2.7-2.8%).