Synthesis 2009(13): 2267-2277  
DOI: 10.1055/s-0029-1216830
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

The Catalytic Potential of 4-Guanidinylpyridines in Acylation Reactions

Ingmar Held, Evgeny Larionov, Christian Bozler, Felicia Wagner, Hendrik Zipse*
Department of Chemistry and Biochemistry, LMU München, 81377 München, Germany
Fax: +49(89)218077738; e-Mail: zipse@cup.uni-muenchen.de;
Further Information

Publication History

Received 3 March 2009
Publication Date:
19 May 2009 (eFirst)

Abstract

A series of 3-alkyl-4-guanidinylpyridines with variable alkylation pattern have been synthesized and characterized with respect to their catalytic potential in acylation reactions of alcohols. The ability of the substitution pattern to stabilize acylpyridinium cations, which act as critical intermediates in the catalytic cycle of pyridine-catalyzed acylation reactions, has been assessed at the MP2(FC)/6-31+G(2d,p)//B98/6-31G(d) level of theory and inclusion of solvent effects in chloroform using the PCM continuum solvation model. The most active 4-guanidinylpyridines are among those having the most electron-rich pyridine ring. The influence of the type and concentration of the auxiliary base on the catalytic activity has also been studied. While the change from triethylamine to N,N-diisopropylethylamine as the auxiliary base does not lead to a systematic increase or decrease in the catalytic rates, the complete absence of auxiliary base leads to a 27-fold reduction in reaction rate.

    References

  • 1 Otera J. Esterification: Methods, Reactions and Applications   Wiley-VCH; Weinheim: 2003. 
  • For reviews see:
  • 2a Höfle G. Steglich W. Vorbrüggen H. Angew. Chem., Int. Ed. Engl.  1978,  17:  569 ; Angew. Chem. 1978, 90, 602
  • 2b Scriven EFV. Chem. Soc. Rev.  1983,  129 
  • 2c Hassner A. In Encyclopedia of Reagents for Organic Synthesis   Wiley; Chichester: 1995.  p.2022-2024 
  • 2d Ragnarsson U. Grehn L. Acc. Chem. Res.  1998,  31:  494 
  • 2e Spivey AC. Maddaford A. Redgrave A. Org. Prep. Proced. Int.  2000,  32:  331 
  • 2f Berry DJ. Digiovanna CV. Metrick SS. Murugan R. ARKIVOC  2001,  (i):  201 
  • 2g Spivey AC. Arseniyadis S. Angew. Chem. Int. Ed.  2004,  43:  5436 ; Angew. Chem. 2004, 116, 5552
  • 3a Kawabata T. Muramatsu W. Nishio T. Shibata T. Uruno Y. Stragies R. Synthesis  2008,  747 
  • 3b Muramatsu W. Kawabata T. Tetrahedron Lett.  2007,  48:  5031 
  • 3c Kawabata T. Muramatsu W. Nishio T. Shibata T. Schedel H. J. Am. Chem. Soc.  2007,  129:  12890 
  • 4a Lewis CA. Miller S. Angew. Chem. Int. Ed.  2006,  45:  5616 
  • 4b Griswold KS. Miller SJ. Tetrahedron  2003,  59:  8869 
  • 5 Kattnig E. Albert M. Org. Lett.  2004,  6:  945 
  • 6a Kurahashi T. Mizutani T. Yoshida J. J. Chem. Soc., Perkin Trans. 1  1999,  465 
  • 6b Kurahashi T. Mizutani T. Yoshida J. Tetrahedron  2002,  58:  8669 
  • 7 Wurz RP. Chem. Rev.  2007,  107:  5570 
  • 8 Hassner A. Krepski LR. Alexanian V. Tetrahedron  1978,  34:  2069 
  • 9 Heinrich MR. Klisa HS. Mayr H. Steglich W. Zipse H. Angew. Chem. Int. Ed.  2003,  42:  4826 ; Angew. Chem. 2003, 115, 4975
  • 10 Held I. Villinger A. Zipse H. Synthesis  2005,  1425 
  • 11 Brotzel F. Kempf B. Singer T. Zipse H. Mayr H. Chem. Eur. J.  2007,  13:  336 
  • 12 Xu S. Held I. Kempf B. Mayr H. Steglich W. Zipse H. Chem. Eur. J.  2005,  11:  4751 
  • 13 Turner JA. J. Org. Chem.  1983,  48:  3401 
  • 14 Isobe T. Ishikawa T. J. Org. Chem.  1999,  64:  6984 
  • 15 Tang Z. Jiang F. Cui X. Gong L.-Z. Mi A.-Q. Jiang Y.-Z. Wu Y.-D. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5755 
  • 16 Gryko D. Lipinski R. Eur. J. Org. Chem.  2006,  3864 
  • 17 Isobe T. Fukuda K. Ishikawa T. J. Org. Chem.  2000,  65:  7770 
  • 18 Held I. Xu S. Zipse H. Synthesis  2007,  1185 
  • 19 Sakakura A. Kawajiri K. Ohkubo T. Kosugi Y. Ishihara K. J. Am. Chem. Soc.  2007,  129:  14775 
  • 20 Lamaty G. Mary F. Roque JP. J. Chim. Phys. Phys.-Chim. Biol.  1991,  88:  1793 
  • 21 Müller CE. Wanka L. Jewell K. Schreiner PR. Angew. Chem. Int. Ed.  2008,  47:  6180 
  • 22a Spivey AC. Arseniyadis S. Fekner T. Maddaford A. Leese DP. Tetrahedron  2006,  62:  295 
  • 22b Spivey AC. Leese DP. Zhu F. Daveya SG. Jarvest RL. Tetrahedron  2004,  60:  4513 
  • 22c Spivey AC. Zhu F. Mitchell MB. Davey SG. Jarvest RL. J. Org. Chem.  2003,  68:  7379 
  • 23 Kagan HB. Fiaud JC. Top. Stereochem.  1988,  18:  249 
  • 24 Gaussian 03, Revision C.02.   Gaussian Inc.; Wallingford CT: 2004. 
  • 25 Kantlehner W. Greiner U. Synthesis  1979,  339 
  • 26 Isobe T, and Keiko F. inventors; JP  10,120,678.  1998
  • 27 Cancès MT. Mennucci B. Tomasi J. J. Chem. Phys.  1997,  107:  3032 
  • 28 Mennucci B. Tomasi J. J. Chem. Phys.  1997,  106:  5151 
  • 29 Cossi M. Barone V. Mennucci B. Tomasi J. Chem. Phys. Lett.  1998,  286:  253 
  • 30a Amovilli C. Barone V. Cammi R. Cances E. Cossi M. Mennucci B. Pomelli CS. Tomasi J. Adv. Quantum Chem.  1998,  32:  227 
  • 30b Cossi M. Scalmani G. Rega N. Barone V. J. Chem. Phys.  2002,  117:  43 
31

Use of the data points describing acetylation of the guanidinyl group leads to an inferior correlation described by the equation ΔH 298 = -3.960 ln(1/t 1/2) - 91.13 kJ/mol; R² = 0.28.