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Synthesis 2012(1): 66-69  
DOI: 10.1055/s-0031-1289527
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© Georg Thieme Verlag Stuttgart ˙ New York

Nanoporous Gold-Catalyzed [4+2] Benzannulation between ortho-Alkynylbenzaldehydes and Alkynes

Naoki Asao*a, Menggenbateerb, Yohei Seyac, Yoshinori Yamamoto*a, Mingwei Chena, Wei Zhangd, Akihisa Inoued
a WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
Fax: +81(22)2176165; e-Mail: asao@m.tohoku.ac.jp; e-Mail: yoshi@m.tohoku.ac.jp;
b Center for Integrated NanoTechnology Support, Tohoku University, Sendai 980-8577, Japan
c Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
d Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
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Publikationsverlauf

Received 1 August 2011
Publikationsdatum:
19. Oktober 2011 (online)

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Abstract

Nanoporous gold material exhibits a catalytic activity on the benzannulation reaction between ortho-alkynylbenzaldehydes and alkynes. The catalyst is easily recoverable and can be reused several times without leaching and loss of activity.

Key words

nanoporous gold - benzannulation - nanostructures - catalysis - cycloaddition

    References and Notes

  • 1a Forty AJ. Nature (London)  1979,  282:  597 
    Google Scholar
  • 1b Erlebacher J. Aziz M. Karma A. Nature (London)  2001,  410:  450 
    Google Scholar
  • 2 Seker E. Reed ML. Begley MR. Materials  2009,  2:  2188 
    Google Scholar
  • 3a Kramer D. Viswanath RN. Weissmueller J. Nano Lett.  2004,  4:  793 
    Google Scholar
  • 3b Biener J. Wittstock A. Zepeda-Ruiz LA. Biener MM. Zielasek V. Dramer D. Viswanath RN. Weissmüller J. Bäumer M. Hamza AV. Nat. Mater.  2009,  8:  47 
    Google Scholar
  • 4a Biener J. Nyce GW. Hodge AM. Biener MM. Hamza AV. Maier SA. Adv. Mater.  2008,  20:  1211 
    Google Scholar
  • 4b Bonroy K. Friedt J.-M. Frederix F. Laureyn W. Langerock S. Campitelli A. Sara M. Borghs G. Goddeeris B. Declerck P. Anal. Chem.  2004,  76:  4299 
    Google Scholar
  • 4c Hieda M. Garcia R. Dixon M. Daniel T. Allara D. Chan MHW. Appl. Phys. Lett.  2004,  84:  628 
    Google Scholar
  • 5a Zielasek V. Jürgens B. Schulz C. Biener J. Biener MM. Hamza AV. Bäumer M. Angew. Chem. Int. Ed.  2006,  45:  8241 
    Google Scholar
  • 5b Xu C. Su J. Xu X. Liu P. Zhao H. Tian F. Ding Y. J. Am. Chem. Soc.  2007,  129:  42 
    Google Scholar
  • 5c Xu C. Xu X. Su J. Ding Y. J. Catal.  2007,  252:  243 
    Google Scholar
  • 5d Wittstock A. Neumann B. Schaefer A. Dumbuya K. Kübel C. Biener MM. Zielasek V. Steinrück H.-P. Gottfried JM. Biener J. Hamza A. Bäumer M. J. Phys. Chem. C  2009,  113:  5593 
    Google Scholar
  • 5e Wanga LC. Jin HJ. Widmann D. Weissmuller J. Behm RJ. J. Catal.  2011,  278:  219 
    Google Scholar
  • 6a Wittstock A. Zielasek V. Biener J. Friend CM. Bäumer M. Science  2010,  327:  319 
    Google Scholar
  • 6b Xu B. Haubrich J. Baker TA. Kaxiras E. Friend CM. J. Phys. Chem. C  2011,  115:  3703 
    Google Scholar
  • 7 Han D. Xu T. Su J. Xu X. Ding Y. ChemCatChem  2010,  2:  383 
    Google Scholar
  • 8 Yin H. Zhou C. Xu C. Liu P. Xu X. Ding Y. J. Phys. Chem. C  2008,  112:  9673 
    Google Scholar
  • 9a Zhang J. Liu P. Ma H. Ding Y. J. Phys. Chem. C  2007,  111:  10382 
    Google Scholar
  • 9b Yu C. Jia F. Ai Z. Zhang L. Chem. Mater.  2007,  19:  6065 
    Google Scholar
  • 9c Zeis R. Lei T. Sieradzki K. Snyder J. Erlebacher J. J. Catal.  2008,  253:  132 
    Google Scholar
  • 10a Asao N. Ishikawa Y. Hatakeyama N. . Yamamoto Y. Chen M. Zhang W. Inoue A. Angew. Chem. Int. Ed.  2010,  49:  10093 
    Google Scholar
  • For the PdNPore-catalyzed reaction, see:
  • 10b Tanaka S. Kaneko T. Asao N. Yamamoto Y. Chen M. Zhang W. Inoue A. Chem. Commun.  2011,  47:  5985 
    Google Scholar
  • Benzannulation with other heterogeneous gold catalysts has been reported, see:
  • 11a Abad A. Corma A. García H. Top. Catal.  2007,  44:  237 
    Google Scholar
  • 11b Organ MG. Shore G. Tsimerman M. Beilstein J. Org. Chem.  2009,  5:  No. 35 
    Google Scholar
  • 11c Shore G. Organ MG. Gold Bull.  2010,  43:  105 
    Google Scholar
  • 12a Asao N. Takahashi K. Lee S. Kasahara T. Yamamoto Y. J. Am. Chem. Soc.  2002,  124:  12650 
    Google Scholar
  • 12b Asao N. Nogami T. Lee S. Yamamoto Y. J. Am. Chem. Soc.  2003,  125:  10921 
    Google Scholar
  • 12c Asao N. Synlett  2006,  1645 
    Google Scholar
  • Recent reviews for the gold-catalyzed reactions, see:
  • 13a Corma A. Leyva-Pérez A. Sabater MJ. Chem. Rev.  2011,  111:  1657 
    Google Scholar
  • 13b Vinod CP. Wilson K. Lee AF.
    J. Chem. Technol. Biotechnol.  2011,  86:  161 
    Google Scholar
  • 13c Yamamoto Y. Gridnev ID. Patil NT. Jin T. Chem. Commun.   2009,  5075 
    Google Scholar
  • 13d Patil NT. Yamamoto Y. Chem. Rev.  2008,  108:  3395 
    Google Scholar
  • 14a Qian LH. Chen MW. Appl. Phys. Lett.  2007,  91:  083105 
    Google Scholar
  • 14b Lang XY. Guan PF. Zhang L. Fujita T. Chen MW. J. Phys. Chem. C  2009,  113:  10956 
    Google Scholar
15

The catalyst is reusable beyond the second reuse, but the reaction time tends to be longer for completion, probably owing to the gradual coarsening of the porous structure.

16

General Procedure
To a mixture of o-alkynylbenzaldehyde 1 (0.2 mmol) and nanoporous gold (20 mol%) in o-C6H4Cl2 (0.5 mL) was added alkyne compound 2 (1.2 mmol) at r.t. under Ar atmosphere. The mixture was stirred for 2.5 h at 150 ˚C and cooled down to r.t. The liquid moiety was separated by a pipette and evaporated to leave the crude product, which was purified by silica gel column chromatography using hexane-EtOAc as eluent to give the pure product 3. The recovered catalyst was washed with Et2O several times, dried under reduced pressure, and reused without further purification.