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;
Further Information

Publication History

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

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.

    References

  • 1 Wöhler F. Liebig F. Ann. Pharm.  1832,  3:  249 
  • For recent reviews see:
  • 2a Moore JL. Rovis T. Top. Curr. Chem.  2009,  291:  77 
  • 2b Enders D. J. Org. Chem.  2008,  73:  7857 
  • 2c Rovis T. Chem. Lett.  2008,  37:  1 
  • 2d Zeitler K. Ernst Schering Found. Symp. Proc.  2007,  2:  183 
  • 2e Enders D. Niemeier O. Henseler A. Chem. Rev.  2007,  107:  5506 
  • 2f Marion N. Diez-Gonzalez S. Nolan SP. Angew. Chem. Int. Ed.  2007,  46:  2988 
  • 2g Zeitler K. Angew. Chem. Int. Ed.  2005,  44:  7506 
  • 2h Christmann M. Angew. Chem. Int. Ed.  2005,  44:  2632 
  • 2i Enders D. Balensiefer T. Acc. Chem. Res.  2004,  37:  534 
  • 2j Johnson JS. Angew. Chem. Int. Ed.  2004,  43:  1326 
  • 3 Ukai T. Tanaka R. Dokawa T. J. Pharm. Soc. Jpn.  1943,  63:  269 
  • 4 Breslow R. J. Am. Chem. Soc.  1958,  80:  3719 
  • 5 Leeper later carried out a detailed kinetic study of the process, see: White MJ. Leeper FJ. J. Org. Chem.  2001,  66:  5124 
  • 6a Enders D. Breuer K. Teles JH. Helv. Chim. Acta  1996,  79:  1217 
  • 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 
  • 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 
  • For selected examples of thiazolium precatalyst mediated asymmetric BC reactions, see:
  • 7a Sheehan J. Hunnemann DH. J. Am. Chem. Soc.  1966,  88:  3666 
  • 7b Sheehan J. Hara T. J. Org. Chem.  1974,  39:  1196 
  • 7c Dvorak CA. Rawal VH. Tetrahedron Lett.  1998,  39:  2925 
  • 7d Takagi W. Tamura Y. Yano Y. Bull. Chem. Soc. Jpn.  1980,  53:  478 
  • 7e Marti J. Castells J. López-Calahora F. Tetrahedron Lett.  1993,  34:  521 
  • 7f Tachibana Y. Kihara N. Takata T. J. Am. Chem. Soc.  2004,  126:  3438 
  • 7g Knight RL. Leeper FJ. Tetrahedron Lett.  1997,  38:  3611 
  • 7h Gerhard AU. Leeper FJ. Tetrahedron Lett.  1997,  38:  3615 
  • 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 
  • 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 
  • 8b Enders D. Han J. Tetrahedron: Asymmetry  2008,  19:  1367 
  • 8c Ma Y. Wei S. Wu J. Yang F. Liu B. Lan J. Yang S. You J. Adv. Synth. Catal.  2008,  350:  2645 
  • 8d O’Toole SE. Connon SJ. Org. Biomol. Chem.  2009,  7:  3584 
  • 8e Baragwanath L. Rose CA. Zeitler K. Connon SJ. J. Org. Chem.  2009,  74:  9214 
  • 8f Brand JP. Siles J. I. O.. Waser J. Synlett  2010,  881 
  • 9 Ide WS. Buck JS. Org. React.  1948,  4:  269 
  • 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 
  • 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 
  • 12b Takikawa H. Hachisu Y. Bode JW. Suzuki K. Angew. Chem. Int. Ed.  2006,  45:  3492 
  • 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 
  • 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 
  • 13 Enders D. Henseler A. Adv. Synth. Catal.  2009,  351:  1749 
  • 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 
  • 15 For an extension of this methodology to include ketimine substrates, see: Enders D. Henseler A. Lowins S. Synthesis  2009,  4125 
  • 16a Kuriakose S. Rajasekharan Pillai VN. Eur. Polym. J.  1994,  30:  881 
  • 16b Kuriakose S. Rajasekharan Pillai VN. Angew. Makromol. Chem.  1994,  221:  53 
  • 16c Kuriakose S. Rajasekharan Pillai VN. Polymer  1994,  35:  1339 
  • 16d Linghu X. Johnson JS. Angew. Chem. Int. Ed.  2003,  42:  2534 
  • 16e Linghu X. Potnick JR. Johnson JS. J. Am. Chem. Soc.  2004,  126:  3070 
  • 16f Bausch CC. Johnson JS. J. Org. Chem.  2004,  69:  4283 
  • 16g Linghu X. Bausch CC. Johnson JS. J. Am. Chem. Soc.  2005,  127:  1833 
  • 16h Tarr JC. Johnson JS. Org. Lett.  2009,  11:  3870 
  • 16i Demir AS. Esiringü I. Göllü M. Reis . J. Org. Chem.  2009,  74:  2197 
  • 16j Demir AS. Reis B. Reis . Eymür S. Göllü M. Tural S. Saglam G. J. Org. Chem.  2007,  72:  7439 
  • 16k Demir AS. Reis . Esiringü I. Reis B. Baris S. Tetrahedron  2007,  63:  160 
  • 16l Demir AS. Reis . Cigdem C. Esiringü I. Eymur S. J. Org. Chem.  2005,  70:  10584 
  • 16m Bausch CC. Johnson JS. Adv. Synth. Catal.  2005,  347:  1207 
  • 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 
  • 16p Mattson AE. Scheidt KA. J. Am. Chem. Soc.  2007,  129:  4508 
  • 17a Lehwald P. Richter M. Röhr C. Liu H.-W. Müller M. Angew. Chem. Int. Ed.  2010,  49:  2389 
  • 17b Müller M. Gocke D. Pohl M. FEBS J.  2009,  276:  2894 
  • 17c Gocke D. Nguyen CL. Pohl M. Stillger T. Walter L. Müller M. Adv. Synth. Catal.  2007,  349:  1425 
  • 17d Demir AS. Şeºengolu . Dünkelmann P. Müller M. Org. Lett.  2003,  5:  2047 
  • 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 
  • 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 
  • 17g Pohl M. Lingen B. Müller M. Chem. Eur. J.  2002,  8:  5288 
  • 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 
  • 20 Vora HU. Lathrop SP. Reynolds NT. Kerr MT. Read de Alaniz J. Rovis T. Org. Synth.  2010,  87:  350 
  • 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)].