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Synlett 2008(16): 2487-2490  
DOI: 10.1055/s-2008-1078259
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Esters Catalyzed by Dicationic Palladium(II)-Chiraphos Complex for Short-Step Synthesis of SmithKline Beecham’s Endothelin Receptor Antagonist

Takashi Nishikataa, Shunsuke Kiyomurab, Yasunori Yamamotob, Norio Miyaura*b
a Innovation Plaza Hokkaido, Japan Science and Technology Agency, Sapporo 060-0819, Japan
b Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
Fax: +81(11)7066561; e-Mail: miyaura@eng.hokudai.ac.jp;
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Publication History

Received 13 June 2008
Publication Date:
21 August 2008 (online)

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Abstract

An asymmetric 1,4-addition of arylboronic acids to RCH=CHCO2Ar (Ar = Ph or 4-acetylphenyl) was carried out at 50 ˚C in aqueous acetone in the presence of [Pd(chiraphos)(PhCN)2](SbF6)2. The reaction gave optically active β-aryl esters in up to 98% ee. The protocol provided a simple access to an endothelin receptor antagonist reported by SmithKline Beecham.

Key words

arylboronic acids - palladium catalyst - asymmetric reaction - conjugate addition - β-arylalkanoate - bioactive compound

    References and Notes

  • 1a Kurihara K. Sugishita N. Oshita K. Piao D. Yamamoto Y. Miyaura N. J. Organomet. Chem.  2007,  692:  428 
    Search in Google Scholar
  • 1b Hayashi T. Yamasaki K. Chem. Rev.  2003,  103:  2829 
    Search in Google Scholar
  • 1c Takaya Y. Ogasawara M. Hayashi T. Sakai M. Miyaura N. J. Am. Chem. Soc.  1998,  120:  5579 
    Search in Google Scholar
  • 2a He P. Lu Y. Dong C.-G. Hu Q.-S. Org. Lett.  2007,  9:  343 
    Search in Google Scholar
  • 2b Lin S. Lu X. Tetrahedron Lett.  2006,  47:  7167 
    Search in Google Scholar
  • 2c Denmark SE. Amishiro N. J. Org. Chem.  2003,  68:  6997 
    Search in Google Scholar
  • 2d Nishikata T. Yamamoto Y. Miyaura N. Angew. Chem. Int. Ed.  2003,  42:  2768 
    Search in Google Scholar
  • 2e Ohe K. Uemura S. Bull. Chem. Soc. Jpn.  2003,  76:  1423 
    Search in Google Scholar
  • 2f For a mechanistic study, see: Nishikata T. Yamamoto Y. Miyaura N. Organometallics  2004,  23:  4317 
    Search in Google Scholar
  • 3a Zhang T. Shi M. Chem. Eur. J.  2008,  14:  3759 
    Search in Google Scholar
  • 3b Song J. Shen Q. Xu F. Lu X. Org. Lett.  2007,  9:  2947 
    Search in Google Scholar
  • 3c Sieber JD. Liu S. Morken JP. J. Am. Chem. Soc.  2007,  129:  2214 
    Search in Google Scholar
  • 3d Suzuma Y. Yamamoto T. Ohta T. Ito Y. Chem. Lett.  2007,  36:  470 
    Search in Google Scholar
  • 3e Gini F. Hessen B. Minnaard AJ. Org. Lett.  2005,  7:  5309 
    Search in Google Scholar
  • 4a Yamamoto Y. Nishikata T. Miyaura N. Pure Appl. Chem.  2008,  80:  807 
    Search in Google Scholar
  • 4b Nishikata T. Yamamoto Y. Miyaura N. Adv. Synth. Catal.  2007,  349:  1759 
    Search in Google Scholar
  • 4c Nishikata T. Yamamoto Y. Gridnev ID. Miyaura N. Organometallics  2005,  24:  5025 
    Search in Google Scholar
  • 4d Nishikata T. Yamamoto Y. Miyaura N. Chem. Lett.  2005,  34:  720 
    Search in Google Scholar
  • 4e Nishikata T. Yamamoto Y. Miyaura N. Chem. Commun.  2004,  1822 
  • For application of Pd-catalyzed 1,4-addition reaction, see:
  • 4f Kobayashi K. Nishikata T. Yamamoto Y. Miyaura N. Bull. Chem. Soc. Jpn.  2008,  in press
  • 4g Nishikata T. Yamamoto Y. Miyaura N. Tetrahedron Lett.  2007,  48:  4007 
    Search in Google Scholar
  • 4h Nishikata T. Yamamoto Y. Miyaura N. Chem. Lett.  2007,  36:  1442 
    Search in Google Scholar
  • 4i Nishikata T. Kobayashi Y. Kobayashi K. Yamamoto Y. Miyaura N. Synlett  2007,  3055 
  • 4j Itoh T. Mase T. Nishikata T. Iyama T. Tachikawa H. Kobayashi Y. Yamamoto Y. Miyaura N. Tetrahedron  2006,  62:  9610 
    Search in Google Scholar
  • 5a Du X. Suguro M. Hirabayashi K. Mori A. Nishikata T. Hagiwara N. Kawata K. Okeda T. Wang H.-F. Fugami K. Kosugi M. Org. Lett.  2001,  3:  3313 
    Search in Google Scholar
  • 5b Cho CS. Motofusa S. Uemura S. Tetrahedron Lett.  1994,  35:  1739 
    Search in Google Scholar
  • 6 Mori A. Danda Y. Fujii T. Hirabayashi K. Osakada K. J. Am. Chem. Soc.  2001,  123:  10774 
    CrossrefPubMedSearch in Google Scholar
  • 7 Koike T. Du X. Sanada T. Danda Y. Mori A. Angew. Chem. Int. Ed.  2003,  42:  89 
    CrossrefPubMedSearch in Google Scholar
  • 8 Farrington EJ. Brown JM. Barnard CFJ. Rowsell E. Angew. Chem. Int. Ed.  2002,  41:  169 
    CrossrefPubMedSearch in Google Scholar
  • 9 Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
    Search in Google Scholar
  • 10 Arai Y. Ueda K. Xie J. Masaki Y. Chem. Pharm. Bull.  2001,  49:  1609 
    CrossrefPubMedSearch in Google Scholar
  • 11a Clark WM. Tickner-Eldridge AM. Huang GK. Pridgen LN. Olsen MA. Mills RJ. Lantos I. Baine NH. J. Am. Chem. Soc.  1998,  120:  4550 
    Search in Google Scholar
  • 11b Elliott JD. Amparo M. Cousins RD. Gao A. Leber JD. Erhard KF. Nambi P. Elshourbagy NA. Kumar C. Lee JA. Bean JW. Brooks CP. Feuerstein G. Ruffolo RR., Jr. Weinstock J. Gleason JG. Peishoff CE. Ohlstein EH. J. Med. Chem.  1994,  37:  1553 
    Search in Google Scholar
  • 12a Kato Y. Niiyama K. Nemoto T. Jona H. Akao A. Okada S. Song ZJ. Zhao M. Tsuchiya Y. Tomimoto K. Mase T. Tetrahedron  2002,  58:  3409 
    Search in Google Scholar
  • 12b Song ZJ. Zhao M. Frey J. Li L. Tan CY. Chen DM. Tschaen R. Tillyer EJJ. Grabowski L. Volante R. Reider PJ. Kato Y. Okada S. Nemoto T. Sato H. Akao A. Mase T. Org. Lett.  2001,  3:  3357 
    Search in Google Scholar
13

General Procedure: A flask charged with [Pd((S,S)-chiraphos)(PhCN)2](SbF6)2 [(S,S)-3; 1 mol%], ArB(OH)2 (1.5 mmol) and 1 (0.5 mmol) was flushed with nitrogen. Acetone (2 mL) and H2O (0.2 mL) were then added. After stirring for 20 h at 50 ˚C, the product was isolated by chromatography on silica gel. The enantiomer excess was determined by Chiral HPLC using Daicel Chiralpak IA, IB or IC.