Download PDF
Synthesis 2011(10): 1515-1525  
DOI: 10.1055/s-0030-1260006
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Hydrogen Peroxide and Arenediazonium Salts as Reagents for a Radical Beckmann-Type Rearrangement

Agnes Prechter, Markus R. Heinrich*
Department für Chemie und Pharmazie, Pharmazeutische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Schuhstraße 19, 91052 Erlangen, Germany
Fax: +49(9131)8522585 ; e-Mail: Markus.Heinrich@medchem.uni-erlangen.de ;
Further Information

Publication History

Received 20 December 2010
Publication Date:
15 April 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

The reductive ring-opening of hydroperoxides derived from cyclic ketones leads to alkyl radicals which can effectively be trapped by arenediazonium salts. This synthetic transformation yielding azo carboxylic acids or lactams, after a reductive step, can be classified as a radical version of the well-known Beckmann rearrangement. In this article, we present results on the scope, the limitations and possible applications of this new reaction type.

Key words

radical reaction - rearrangement - ketones - carboxylic acids - azo compounds

    References

  • 1 Metzger H. Houben-Weyl   Vol. X/4:  Georg Thieme Verlag; Stuttgart: 1968.  p.1-308  
    Google Scholar
  • 2 For a first report, see: Beckmann E. Ber. Dtsch. Chem. Ges.  1886,  19:  988 
    CrossrefPubMedGoogle Scholar
  • For review articles, see:
  • 3a For a first report, see: Blatt AH. Chem. Rev.  1933,  12:  215 ; and references cited therein
    Google Scholar
  • 3b Jones B. Chem. Rev.  1944,  35:  335 
    Google Scholar
  • 3c Gawley RE. Org. React.  1988,  35:  1 
    Google Scholar
  • 3d Craig D. Comprehensive Organic Synthesis   Vol. 7:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.689 ; and references cited therein
    Google Scholar
  • 3e Smith MB. March J. March’s Advanced Organic Chemistry   6th ed.:  John Wiley & Sons; Hoboken: 2007.  p.1613 
    Google Scholar
  • 4 Hendrickson JB. Cram DJ. Hammond GS. Organic Chemistry   3rd ed.:  McGraw-Hill; Tokyo: 1970.  p.708 
    Google Scholar
  • 5 For the use of SOCl2, see: Butler RN. O’Donoghue DA. J. Chem. Res., Synop.  1983,  18 
    Google Scholar
  • 6 For rearrangements of oxime p-toluenesulfonates using silica gel, see: Costa A. Mestres R. Riego JM. Synth. Commun.  1982,  12:  1003 
    CrossrefGoogle Scholar
  • 7 For a report on the application of MoO3 on silica gel, see: Dongare MK. Bhagwat VV. Ramana CV. Gurjar MK. Tetrahedron Lett.  2004,  45:  4759 
    CrossrefGoogle Scholar
  • 8 For the use of montmorillonite KSF, see: Meshram HM. Synth. Commun.  1990,  20:  3253 
    CrossrefGoogle Scholar
  • 9 For RuCl3-mediated Beckmann rearrangements, see: De S K. Synth. Commun.  2004,  34:  3431 
    CrossrefGoogle Scholar
  • 10 For Y(OTf)3-mediated Beckmann rearrangements, see: De S K. Org. Prep. Proced. Int.  2004,  36:  383 
    CrossrefGoogle Scholar
  • 11 For BiCl3-mediated Beckmann rearrangements, see: Thakur AJ. Boruah A. Prajapati D. Sandhu JS. Synth. Commun.  2000,  30:  2105 
    CrossrefGoogle Scholar
  • 12 For the use of 2,4,6-trichloro-1,3,5-triazine, see: Luca LD. Giacomelli G. Porcheddu A. J. Org. Chem.  2002,  67:  6272 
    CrossrefGoogle Scholar
  • 13 For Ga(OTf)3-mediated Beckmann rearrangements, see: Yan P. Batamack P. Prakash GKS. Olah GA. Catal. Lett.  2005,  103:  165 
    CrossrefGoogle Scholar
  • For the use of rare earth exchanged zeolites, see:
  • 14a Thomas B. Prathapan S. Sugunan S. Microporous Mesoporous Mater.  2005,  84:  137 
    Google Scholar
  • 14b Thomas B. Sugunan S. Microporous Mesoporous Mater.  2006,  96:  55 
    Google Scholar
  • 15a Zhang Z. Li J. Yang X. Catal. Lett.  2007,  118:  300 
    Google Scholar
  • 15b Li Z.  Lu Z.  Ding R.  Yang J. J. Chem. Res.  2006,  668 
    Google Scholar
  • 15c Priya SV. Mabel JH. Palanichamy M. Murugesan V. Stud. Surf. Sci. Catal.  2008,  174:  1147 
    Google Scholar
  • For Beckmann rearrangements in the vapor phase, see:
  • 16a Maheswari R. Shanthi K. Sivakumar T. Narayanan S. Appl. Catal., A  2003,  248(1-2):  291 
    Google Scholar
  • 16b Mao D. Chen Q. Lu G. Appl. Catal., A  2003,  244(2):  273 
    Google Scholar
  • 16c Izumi Y. Ichihashi H. Shimazu Y. Kitamura M. Sato H. Bull. Chem. Soc. Jpn.  2007,  80:  1280 
    Google Scholar
  • For Beckmann rearrangements in supercritical water, see:
  • 17a Ikushima Y. Hatakeda K. Sato O. Yokoyama T. Arai M. J. Am. Chem. Soc.  2000,  122:  1908 
    Google Scholar
  • 17b Boero M. Ikeshoji T. Liew CC. Terakura K. Parrinello M. J. Am. Chem. Soc.  2004,  126:  6280 
    Google Scholar
  • For Beckmann rearrangements in ionic liquids, see:
  • 18a Peng J. Deng Y. Tetrahedron Lett.  2001,  42:  403 
    Google Scholar
  • 18b Ren RX. Zueva LD. Ou W. Tetrahedron Lett.  2001,  42:  8441 
    Google Scholar
  • 18c Lee JK. Kim D. Song CE. Lee S. Synth. Commun.  2003,  33:  2301 
    Google Scholar
  • 19 For a review on nitrogen-centered radical scavengers, see: Höfling S. Heinrich MR. Synthesis  2011,  173 
    Article in Thieme ConnectGoogle Scholar
  • For sulfonyl azides as N-centered radical scavengers, see:
  • 20a Renaud P. Ollivier C. J. Am. Chem. Soc.  2000,  122:  6496 
    Google Scholar
  • 20b Renaud P. Panchaud P. Chabaud L. Landais Y. Ollivier C. Zigmantas S. Chem. Eur. J.  2004,  10:  3606 
    Google Scholar
  • 20c Renaud P. Kapat A. Nyfeler E. Giuffredi GT. J. Am. Chem. Soc.  2009,  131:  17746 
    Google Scholar
  • For nitroso compounds as N-centered radical scavengers, see:
  • 21a Girard P. Guillot N. Motherwell WB. Potier P. J. Chem. Soc., Chem. Commun.  1995,  2385 
    Google Scholar
  • 21b Girard P. Guillot N. Motherwell WB. Hay-Motherwell RS. Potier P. Tetrahedron  1999,  55:  3573 
    Google Scholar
  • For imines as N-centered radical scavengers, see:
  • 22a Ryu I. Matsu K. Minakata S. Komatsu M. J. Am. Chem. Soc.  1998,  120:  5838 
    Google Scholar
  • 22b Lamas C.-M. Vaillard SE. Wibbeling B. Studer A. Org. Lett.  2010,  12:  2072 
    Google Scholar
  • For azo compounds as N-centered radical scavengers, see:
  • 23a Alberti A. Bedogni N. Benaglia M. Leardini R. Nanni D. Pedulli GF. Tundo A. Zanardi G. J. Org. Chem.  1992,  57:  607 
    Google Scholar
  • 23b Baigrie BD. Cadogan JIG. Sharp JT. J. Chem. Soc., Perkin Trans. 1  1975,  1029 
    Google Scholar
  • For diazirines as N-centered radical scavengers, see:
  • 24a Barton DHR. Jaszberenyi JC. Theodorakis EA. J. Am. Chem. Soc.  1992,  114:  5904 
    Google Scholar
  • 24b Barton DHR. Jaszberenyi JS. Theodorakis EA. Reibenspies JH.
    J. Am. Chem. Soc.  1993,  115:  8050 
    Google Scholar
  • For recent reports on arenediazonium salts as radical scavengers, see:
  • 25a Heinrich MR. Blank O. Wölfel S. Org. Lett.  2006,  8:  3323 
    Google Scholar
  • 25b Blank O. Heinrich MR. Eur. J. Org. Chem.  2006,  4331 
    Google Scholar
  • 25c Heinrich MR. Blank O. Wetzel A. Synlett  2006,  3352 
    Google Scholar
  • 25d Heinrich MR. Blank O. Wetzel A. J. Org. Chem.  2007,  72:  476 
    Google Scholar
  • 25e Blank O. Wetzel A. Ullrich D. Heinrich MR. Eur. J. Org. Chem.  2008,  3179 
    Google Scholar
  • 26 Criegee R. Houben-Weyl   Vol. VIII:  Georg Thieme Verlag; Stuttgart: 1968.  p.1-74  
    Google Scholar
  • For radical reactions employing hydroperoxides (as radical sources) in combination with arenediazonium salts (as radical scavengers), see:
  • 27a Citterio A. Minisci F. J. Org. Chem.  1982,  47:  1759 
    Google Scholar
  • 27b Blank O. Raschke N. Heinrich MR. Tetrahedron Lett.  2010,  51:  1758 
    Google Scholar
  • For the iron(II) or copper(I)-mediated cleavage of (hydro-)peroxides, see:
  • 29a Walling C. Zavitsas AA.
    J. Am. Chem. Soc.  1963,  85:  2084 
    Google Scholar
  • 29b Walling C. Acc. Chem. Res.  1975,  8:  125 
    Google Scholar
  • 29c Schreiber SL. J. Am. Chem. Soc.  1980,  102:  6163 
    Google Scholar
  • 29d Schreiber SL. Hulin B. Liew W.-F. Tetrahedron  1986,  42:  2945 
    Google Scholar
  • For review articles on oxygen-centered radicals, see:
  • 30a Suárez E. Rodriguez MS. In Radicals in Organic Synthesis   1st ed., Vol. 2:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  p.440 
    Google Scholar
  • 30b Hartung J. Gottwald T. Spehar K. Synthesis  2002,  1469 
    Google Scholar
  • 31a Francisco CG. González CC. Kennedy AR. Paz NR. Suárez E. Chem. Eur. J.  2008,  14:  6704 
    Google Scholar
  • 31b Alonso-Cruz CR. Kennedy AR. Rodriguez MS. Suárez E. Tetrahedron Lett.  2007,  48:  7207 
    Google Scholar
  • 31c Dichtl A. Seyfried M. Schoening K.-U. Synlett  2008,  1877 
    Google Scholar
  • For review articles on arenediazonium salts as sources for aryl radicals, see:
  • 32a Galli C. Chem. Rev.  1988,  88:  765 
    Google Scholar
  • 32b Heinrich MR. Chem. Eur. J.  2009,  15:  820 
    Google Scholar
  • For the formation of diversely substituted carboxylic and dicarboxylic acids from cyclic hydroperoxides upon reduction, see:
  • 33a Cooper W. Davison WHT. J. Chem. Soc.  1952,  1180 
    Google Scholar
  • 33b Hawkins EGE. J. Chem. Soc.  1955,  3463 
    Google Scholar
  • 33c Kharasch MS. Nudenberg W. J. Org. Chem.  1954,  19:  1921 
    Google Scholar
  • 33d Braunwarth JB. Crosby GW. J. Org. Chem.  1962,  27:  2064 
    Google Scholar
  • 33e De La Mare HE. Kochi JK. Rust FF. J. Am. Chem. Soc.  1963,  85:  1437 
    Google Scholar
  • For recent reports on bond strengths and radical stability, see:
  • 34a Zipse H. Top. Curr. Chem.  2006,  263:  163 
    Google Scholar
  • 34b Zavitsas A. J. Org. Chem.  2008,  73:  9022 
    Google Scholar
  • 35 For an example of a temperature-dependent ring-opening reaction, see: Beckwith ALJ. Kazlauskas R. Syner-Lyons MR. J. Org. Chem.  1983,  48:  4718 
    CrossrefGoogle Scholar
  • 36 For a computational study on the regioselectivity of alkoxy radical fragmentation, see: Wilsey S. Dowd P. Houk KN. J. Org. Chem.  1999,  64:  8801 
    CrossrefGoogle Scholar
  • For syntheses of hydroperoxides from cyclic ketones and studies on their structure see
  • 37a Milas NA. Harris SA. Panagiotakos PC. J. Am. Chem. Soc.  1939,  61:  2430 
    Google Scholar
  • 37b Criegee R. Schnorrenberg W. Becke J. Justus Liebigs Ann. Chem.  1949,  565:  7 
    Google Scholar
  • 37c Karasch MS. Sosnovsky G. J. Org. Chem.  1958,  23:  1322 
    Google Scholar
  • 37d Brown N. Hartig MJ. Roedel MJ. Anderson AW. Schweitzer CE. J. Am. Chem. Soc.  1955,  77:  1756 
    Google Scholar
  • 38 For a study on equilibrium data for the formation of cyclic hydroperoxides in dioxane see: Jacobson SE. Mares F. Zambri PM. J. Am. Chem. Soc.  1979,  101:  6938 
    CrossrefGoogle Scholar
  • 40 Röder E. Krauß H. Liebigs Ann. Chem.  1992,  177 
    Google Scholar
  • 41 Heinrich MR. Blank O. Ullrich D. Kirschstein M.
    J. Org. Chem.  2007,  72:  9609 
    CrossrefPubMedGoogle Scholar
  • 42 Elofson RM. Gadallah FF. J. Org. Chem.  1971,  36:  1769 
    CrossrefGoogle Scholar
  • Two rare examples for the preparation of azo carboxylic acids have been reported by
  • 43a Fusco R. Romani R. Gazz. Chim. Ital.  1948,  78:  342 
    Google Scholar
  • 43b Khaimov IN. Trudy Tadzhik. Sel’skokhoz. Inst.  1958,  1:  33 
    Google Scholar
  • 45 The instability of related azo compounds to chromatography was also reported in: Baldwin JE. Adlington RM. Bottaro JC. Kolhe JN. Perry MWD. Jain AU. Tetrahedron  1986,  42:  4223 
    CrossrefGoogle Scholar
  • 46 A mixture was obtained when using classical Beckmann conditions: Schäffler A. Ziegenbein W. Chem. Ber.  1955,  88:  1374 
    CrossrefGoogle Scholar
  • 49 de Vleeschouwer F. van Speybroeck V. Waroquier M. Geerlings P. de Proft F. Org. Lett.  2007,  9:  2721 
    CrossrefGoogle Scholar
  • 50a

    See ref. 25d.

  • 50b Haag BA. Zhang Z. Li J. Knochel P. Angew. Chem. Int. Ed.  2010,  49:  9513 
    Google Scholar
  • 50c Rossiter S. Folkes LK. Wardman P. Bioorg. Med. Chem. Lett.  2002,  12:  2523 
    Google Scholar
  • 51 For a formation of lactams from azo carboxylic esters, see: Baldwin JE. Adlington RM. Jain AU. Kolhe JN. Perry MWD. Tetrahedron  1986,  42:  4247 
    CrossrefGoogle Scholar
  • 52a Molina CL. Chow CP. Shea KJ. J. Org. Chem.  2007,  72:  6816 
    Google Scholar
  • 52b Rautenstrauch V. Delay F. Angew. Chem. Int. Ed.  1980,  19:  726 
    Google Scholar
  • 52c Matsuyama H. Itoh N. Matsumoto A. Ohira N. Hara K. Yoshida M. Iyoda M. J. Chem. Soc., Perkin Trans. 1  2001,  2924 
    Google Scholar
  • 52d Fernández R. Ferrete A. Llera JM. Magriz A. Martín-Zamora E. Díez E. Lassaletta JM. Chem. Eur. J.  2004,  10:  737 
    Google Scholar
  • 52e Friestad GK. Qin J. J. Am. Chem. Soc.  2001,  123:  9922 
    Google Scholar
  • 54a Gruner M. Pfeifer D. Becker HGO. Radeglia R. Epperlein J. J. Prakt. Chem.  1985,  327:  63 
    Google Scholar
  • 54b Bahr JL. Yang J. Kosynkin DV. Bronikowski MJ. Smalley RE. Tour JM. J. Am. Chem. Soc.  2001,  123:  6536 
    Google Scholar
  • 55 Burnell DJ. Wu Y. Can. J. Chem.  1990,  68:  804 
    CrossrefGoogle Scholar
  • 56 Haynes RK. King GR. Vonwiller SC. J. Org. Chem.  1994,  59:  4743 
    CrossrefGoogle Scholar
  • 57a Golding BT. Bleasdale C. McGinnis J. Müller S. Rees HT. Rees NH. Farmer PB. Watson WP. Tetrahedron  1997,  53:  4063 
    Google Scholar
  • 57b Snyder JK. Stock LM. J. Org. Chem.  1980,  45:  886 
    Google Scholar
  • 58a Takemiya A. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  14800 
    Google Scholar
  • 58b Schmidt AM. Eilbracht P. Org. Biomol. Chem.  2005,  3:  2333 
    Google Scholar
  • 59 Bullock MW. Fox SW. J. Am. Chem. Soc.  1951,  73:  5155 
    CrossrefGoogle Scholar
  • 60 Ramalingan C. Park Y.-T. Synthesis  2008,  1351 
    Article in Thieme ConnectGoogle Scholar
28

For hydrogenolytic cleavage of N=N bonds, see ref. 25a and 25e.

39

For reports of varying yields of dodecanedioic acid dependent on the composition of peroxide, see ref. 33b and 37c.

44

After column chromatography on silica gel, a number of new compounds were detected that had not been present before. Several attempts including the variation of solvents and the use of deactivated silica gel were unsuccessful in preventing the partial decomposition of the azo carboxylic acids 9. Independent NMR experiments pointed to the formation of hydrazones as first intermediates of the decomposition pathway.

47

Better selectivities can be observed with the newly developed reagents, see refs. 8, 11, 12 and 13.

48

Exceptions are carboxylic acids 9ac, 9da, and 9ha, which were accompanied by hydrazones in the ratios 9/hydrazone 2:1, 3:1, and 2:1, respectively.

53

The literature procedure given in ref. 52d was slightly modified by refluxing the reaction mixture for 4 hours.