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Synthesis 2011(2): 190-198  
DOI: 10.1055/s-0030-1258363
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Chemoselective Crossed Acyloin Condensations: Catalyst and Substrate Control

Christopher A. Rosea, Sivaji Gundalab, Stephen J. Connon*b, Kirsten Zeitler*a
a Institut für Organische Chemie, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany
Fax: +49(941)9434121; e-Mail: kirsten.zeitler@chemie.uni-regensburg.de;
b Centre for Synthesis and Chemical Biology, School of Chemistry, The University of Dublin, Trinity College, Dublin 2, Ireland
Fax: +353(167)12826; e-Mail: connons@tcd.ie;
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Publication History

Received 17 November 2010
Publication Date:
20 December 2010 (online)

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Abstract

The interplay between catalyst and substrate control in crossed acyloin condensation reactions has been studied. It was found that a pentafluorophenyl-substituted triazolium ion derived catalyst was capable of catalyzing highly chemoselective processes between a range of aliphatic and aromatic aldehydes utilized in a 1:1 ratio.

Key words

organic synthesis - carbenes - heterocycles - catalysis - umpolung reactions

    References

  • 1 Wöhler F. Liebig F. Ann. Pharm.  1832,  3:  249 
    Search in Google Scholar
  • For recent reviews see:
  • 2a Moore JL. Rovis T. Top. Curr. Chem.  2009,  291:  77 
    Search in Google Scholar
  • 2b Enders D. J. Org. Chem.  2008,  73:  7857 
    Search in Google Scholar
  • 2c Rovis T. Chem. Lett.  2008,  37:  1 
    Search in Google Scholar
  • 2d Zeitler K. Ernst Schering Found. Symp. Proc.  2007,  2:  183 
    Search in Google Scholar
  • 2e Enders D. Niemeier O. Henseler A. Chem. Rev.  2007,  107:  5506 
    Search in Google Scholar
  • 2f Marion N. Diez-Gonzalez S. Nolan SP. Angew. Chem. Int. Ed.  2007,  46:  2988 
    Search in Google Scholar
  • 2g Zeitler K. Angew. Chem. Int. Ed.  2005,  44:  7506 
    Search in Google Scholar
  • 2h Christmann M. Angew. Chem. Int. Ed.  2005,  44:  2632 
    Search in Google Scholar
  • 2i Enders D. Balensiefer T. Acc. Chem. Res.  2004,  37:  534 
    Search in Google Scholar
  • 2j Johnson JS. Angew. Chem. Int. Ed.  2004,  43:  1326 
    Search in Google Scholar
  • 3 Ukai T. Tanaka R. Dokawa T. J. Pharm. Soc. Jpn.  1943,  63:  269 
    Search in Google Scholar
  • 4 Breslow R. J. Am. Chem. Soc.  1958,  80:  3719 
    Search in Google Scholar
  • 5 Leeper later carried out a detailed kinetic study of the process, see: White MJ. Leeper FJ. J. Org. Chem.  2001,  66:  5124 
    CrossrefSearch in Google Scholar
  • 6a Enders D. Breuer K. Teles JH. Helv. Chim. Acta  1996,  79:  1217 
    Search in Google Scholar
  • 6b Enders D. Breuer K. Raabe G. Runsink J. Teles JH. Melder J.-P. Ebel K. Brode S. Angew. Chem., Int. Ed. Engl.  1995,  34:  1021 
    Search in Google Scholar
  • 6c Teles JH. Melder J.-P. Ebel K. Schneider R. Gehrer E. Harder W. Brode S. Enders D. Breuer K. Raabe G. Helv. Chim. Acta  1996,  79:  61 
    Search in Google Scholar
  • For selected examples of thiazolium precatalyst mediated asymmetric BC reactions, see:
  • 7a Sheehan J. Hunnemann DH. J. Am. Chem. Soc.  1966,  88:  3666 
    Search in Google Scholar
  • 7b Sheehan J. Hara T. J. Org. Chem.  1974,  39:  1196 
    Search in Google Scholar
  • 7c Dvorak CA. Rawal VH. Tetrahedron Lett.  1998,  39:  2925 
    Search in Google Scholar
  • 7d Takagi W. Tamura Y. Yano Y. Bull. Chem. Soc. Jpn.  1980,  53:  478 
    Search in Google Scholar
  • 7e Marti J. Castells J. López-Calahora F. Tetrahedron Lett.  1993,  34:  521 
    Search in Google Scholar
  • 7f Tachibana Y. Kihara N. Takata T. J. Am. Chem. Soc.  2004,  126:  3438 
    Search in Google Scholar
  • 7g Knight RL. Leeper FJ. Tetrahedron Lett.  1997,  38:  3611 
    Search in Google Scholar
  • 7h Gerhard AU. Leeper FJ. Tetrahedron Lett.  1997,  38:  3615 
    Search in Google Scholar
  • 7i Knight RL. Leeper FJ. J. Chem. Soc., Perkin Trans. 1  1998,  1891 
  • 7j Pesch J. Harms K. Bach T. Eur. J. Org. Chem.  2004,  2025 
  • 7k Mennen SM. Gipson JD. Kim YR. Miller SJ. J. Am. Chem. Soc.  2005,  127:  1654 
    Search in Google Scholar
  • For selected examples of triazolium ion mediated asymmetric BC reactions, see ref. 6a, 7i and:
  • 8a Enders D. Kallfass U. Angew. Chem. Int. Ed.  2002,  41:  1743 
    Search in Google Scholar
  • 8b Enders D. Han J. Tetrahedron: Asymmetry  2008,  19:  1367 
    Search in Google Scholar
  • 8c Ma Y. Wei S. Wu J. Yang F. Liu B. Lan J. Yang S. You J. Adv. Synth. Catal.  2008,  350:  2645 
    Search in Google Scholar
  • 8d O’Toole SE. Connon SJ. Org. Biomol. Chem.  2009,  7:  3584 
    Search in Google Scholar
  • 8e Baragwanath L. Rose CA. Zeitler K. Connon SJ. J. Org. Chem.  2009,  74:  9214 
    Search in Google Scholar
  • 8f Brand JP. Siles J. I. O.. Waser J. Synlett  2010,  881 
  • 9 Ide WS. Buck JS. Org. React.  1948,  4:  269 
    Search in Google Scholar
  • 10a Stetter H. Dämbkes G. Synthesis  1977,  403 
  • 10b Stetter H. Dämbkes G. Synthesis  1980,  309 
  • Miller et al. reported one example of a crossed AC reaction using o-tolualdehyde and hexanal mediated by a triazolium ion precatalyst (stoichiometric loadings). The yield of the isolated product was 16%.
  • 11x Mennen S. M. Miller S. J. J. Org. Chem.  2007,  72:  5260 
    Search in Google Scholar
  • Intramolecular enantioselective AC reactions between aldehydes and ketones are known. For representative examples, see:
  • 12a Enders D. Niemeier O. Balensiefer T. Angew. Chem. Int. Ed.  2006,  45:  1463 
    Search in Google Scholar
  • 12b Takikawa H. Hachisu Y. Bode JW. Suzuki K. Angew. Chem. Int. Ed.  2006,  45:  3492 
    Search in Google Scholar
  • 12c Enders D. Niemeier O. Raabe G. Synlett  2006,  2431 
  • 12d Li Y. Feng Z. You S.-L. Chem. Commun.  2008,  2263 
  • 12e Ema T. Oue Y. Akihara K. Miyazaki Y. Sakai T. Org. Lett.  2009,  11:  4866 
    Search in Google Scholar
  • 12f For a recent example in the context of a multicatalytic cascade sequence, see: Lathrop SP. Rovis T. J. Am. Chem. Soc.  2009,  131:  13628 
    Search in Google Scholar
  • 13 Enders D. Henseler A. Adv. Synth. Catal.  2009,  351:  1749 
    CrossrefSearch in Google Scholar
  • 14 For a recent report detailing asymmetric variants of this process, see: Enders D. Grossmann A. Fronert J. Raabe G. Chem. Commun.  2010,  46:  6282 
    Search in Google Scholar
  • 15 For an extension of this methodology to include ketimine substrates, see: Enders D. Henseler A. Lowins S. Synthesis  2009,  4125 
    Thieme Connect
  • 16a Kuriakose S. Rajasekharan Pillai VN. Eur. Polym. J.  1994,  30:  881 
    Search in Google Scholar
  • 16b Kuriakose S. Rajasekharan Pillai VN. Angew. Makromol. Chem.  1994,  221:  53 
    Search in Google Scholar
  • 16c Kuriakose S. Rajasekharan Pillai VN. Polymer  1994,  35:  1339 
    Search in Google Scholar
  • 16d Linghu X. Johnson JS. Angew. Chem. Int. Ed.  2003,  42:  2534 
    Search in Google Scholar
  • 16e Linghu X. Potnick JR. Johnson JS. J. Am. Chem. Soc.  2004,  126:  3070 
    Search in Google Scholar
  • 16f Bausch CC. Johnson JS. J. Org. Chem.  2004,  69:  4283 
    Search in Google Scholar
  • 16g Linghu X. Bausch CC. Johnson JS. J. Am. Chem. Soc.  2005,  127:  1833 
    Search in Google Scholar
  • 16h Tarr JC. Johnson JS. Org. Lett.  2009,  11:  3870 
    Search in Google Scholar
  • 16i Demir AS. Esiringü I. Göllü M. Reis . J. Org. Chem.  2009,  74:  2197 
    Search in Google Scholar
  • 16j Demir AS. Reis B. Reis . Eymür S. Göllü M. Tural S. Saglam G. J. Org. Chem.  2007,  72:  7439 
    Search in Google Scholar
  • 16k Demir AS. Reis . Esiringü I. Reis B. Baris S. Tetrahedron  2007,  63:  160 
    Search in Google Scholar
  • 16l Demir AS. Reis . Cigdem C. Esiringü I. Eymur S. J. Org. Chem.  2005,  70:  10584 
    Search in Google Scholar
  • 16m Bausch CC. Johnson JS. Adv. Synth. Catal.  2005,  347:  1207 
    Search in Google Scholar
  • 16n Mathies AK. Mattson AE. Scheidt KA. Synlett  2009,  377 
  • 16o Mattson AE. Zuhl AM. Reynolds TE. Scheidt KA. J. Am. Chem. Soc.  2006,  128:  4932 
    Search in Google Scholar
  • 16p Mattson AE. Scheidt KA. J. Am. Chem. Soc.  2007,  129:  4508 
    Search in Google Scholar
  • 17a Lehwald P. Richter M. Röhr C. Liu H.-W. Müller M. Angew. Chem. Int. Ed.  2010,  49:  2389 
    Search in Google Scholar
  • 17b Müller M. Gocke D. Pohl M. FEBS J.  2009,  276:  2894 
    Search in Google Scholar
  • 17c Gocke D. Nguyen CL. Pohl M. Stillger T. Walter L. Müller M. Adv. Synth. Catal.  2007,  349:  1425 
    Search in Google Scholar
  • 17d Demir AS. Şeºengolu . Dünkelmann P. Müller M. Org. Lett.  2003,  5:  2047 
    Search in Google Scholar
  • 17e Dünkelmann P. Kolter-Jung D. Nitsche A. Demir AS. Siegert P. Linden B. Baumann M. Pohl M. Müller M. J. Am. Chem. Soc.  2002,  124:  12084 
    Search in Google Scholar
  • 17f Demir AS. Şeºengolu Ö. Eren E. Hosrik B. Pohl M. Janzen E. Kolter D. Feldmann R. Dünkelmann P. Müller M. Adv. Synth. Catal.  2002,  344:  96 
    Search in Google Scholar
  • 17g Pohl M. Lingen B. Müller M. Chem. Eur. J.  2002,  8:  5288 
    Search in Google Scholar
  • 17h Demir AS. Pohl M. Janzen E. Müller M. J. Chem. Soc,. Perkin Trans. 1  2001,  633 
  • 18 O’Toole SE. Rose CA. Gundala S. Zeitler K. Connon SJ. J. Org. Chem.  2010, DOI: 10.1021/jo101791w
  • 19 We have previously reported that thiazolium ions can mediate the oxidation of aldehydes in the presence of a stoichiometric oxidant. Triazolium ions were poor catalysts for this process. In recalcitrant reactions involving 18 and protic solvent it is possible that the presence of adventitious oxygen may be responsible for low product yields: Noonan C. Baragwanath L. Connon SJ. Tetrahedron Lett.  2008,  49:  4003 
    CrossrefSearch in Google Scholar
  • 20 Vora HU. Lathrop SP. Reynolds NT. Kerr MT. Read de Alaniz J. Rovis T. Org. Synth.  2010,  87:  350 
    CrossrefSearch in Google Scholar
  • 22a Stetter H. Rämsch RY. Kuhlmann H. Synthesis  1976,  733 
  • 22b Cumper CWN. Thurston AP. J. Chem. Soc., Perkin Trans. 2  1972,  106 
21

In order to reproduce the conditions on a smaller scale we found a tube-shaped flask better suited to handle smaller amounts of solvent [cf. high concentration of the reactions performed by Stetter (ca. 3 M)].