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

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.

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  

2 For a first report, see: Beckmann E. Ber. Dtsch. Chem. Ges.  1886,  19:  988 

For review articles, see:

3a For a first report, see: Blatt AH. Chem. Rev.  1933,  12:  215 ; and references cited therein

3b Jones B. Chem. Rev.  1944,  35:  335 

3c Gawley RE. Org. React.  1988,  35:  1 

3d Craig D. Comprehensive Organic Synthesis   Vol. 7:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.689 ; and references cited therein

3e Smith MB. March J. March’s Advanced Organic Chemistry   6th ed.:  John Wiley & Sons; Hoboken: 2007.  p.1613 

4 Hendrickson JB. Cram DJ. Hammond GS. Organic Chemistry   3rd ed.:  McGraw-Hill; Tokyo: 1970.  p.708 

5 For the use of SOCl₂, see: Butler RN. O’Donoghue DA. J. Chem. Res., Synop.  1983,  18 

6 For rearrangements of oxime p-toluenesulfonates using silica gel, see: Costa A. Mestres R. Riego JM. Synth. Commun.  1982,  12:  1003 

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 

8 For the use of montmorillonite KSF, see: Meshram HM. Synth. Commun.  1990,  20:  3253 

9 For RuCl₃-mediated Beckmann rearrangements, see: De S K. Synth. Commun.  2004,  34:  3431 

10 For Y(OTf)₃-mediated Beckmann rearrangements, see: De S K. Org. Prep. Proced. Int.  2004,  36:  383 

11 For BiCl₃-mediated Beckmann rearrangements, see: Thakur AJ. Boruah A. Prajapati D. Sandhu JS. Synth. Commun.  2000,  30:  2105 

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 

13 For Ga(OTf)₃-mediated Beckmann rearrangements, see: Yan P. Batamack P. Prakash GKS. Olah GA. Catal. Lett.  2005,  103:  165 

For the use of rare earth exchanged zeolites, see:

14a Thomas B. Prathapan S. Sugunan S. Microporous Mesoporous Mater.  2005,  84:  137 

14b Thomas B. Sugunan S. Microporous Mesoporous Mater.  2006,  96:  55 

15a Zhang Z. Li J. Yang X. Catal. Lett.  2007,  118:  300 

15b Li Z.  Lu Z.  Ding R.  Yang J. J. Chem. Res.  2006,  668 

15c Priya SV. Mabel JH. Palanichamy M. Murugesan V. Stud. Surf. Sci. Catal.  2008,  174:  1147 

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 

16b Mao D. Chen Q. Lu G. Appl. Catal., A  2003,  244(2):  273 

16c Izumi Y. Ichihashi H. Shimazu Y. Kitamura M. Sato H. Bull. Chem. Soc. Jpn.  2007,  80:  1280 

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 

17b Boero M. Ikeshoji T. Liew CC. Terakura K. Parrinello M. J. Am. Chem. Soc.  2004,  126:  6280 

For Beckmann rearrangements in ionic liquids, see:

18a Peng J. Deng Y. Tetrahedron Lett.  2001,  42:  403 

18b Ren RX. Zueva LD. Ou W. Tetrahedron Lett.  2001,  42:  8441 

18c Lee JK. Kim D. Song CE. Lee S. Synth. Commun.  2003,  33:  2301 

19 For a review on nitrogen-centered radical scavengers, see: Höfling S. Heinrich MR. Synthesis  2011,  173 

For sulfonyl azides as N-centered radical scavengers, see:

20a Renaud P. Ollivier C. J. Am. Chem. Soc.  2000,  122:  6496 

20b Renaud P. Panchaud P. Chabaud L. Landais Y. Ollivier C. Zigmantas S. Chem. Eur. J.  2004,  10:  3606 

20c Renaud P. Kapat A. Nyfeler E. Giuffredi GT. J. Am. Chem. Soc.  2009,  131:  17746 

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 

21b Girard P. Guillot N. Motherwell WB. Hay-Motherwell RS. Potier P. Tetrahedron  1999,  55:  3573 

For imines as N-centered radical scavengers, see:

22a Ryu I. Matsu K. Minakata S. Komatsu M. J. Am. Chem. Soc.  1998,  120:  5838 

22b Lamas C.-M. Vaillard SE. Wibbeling B. Studer A. Org. Lett.  2010,  12:  2072 

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 

23b Baigrie BD. Cadogan JIG. Sharp JT. J. Chem. Soc., Perkin Trans. 1  1975,  1029 

For diazirines as N-centered radical scavengers, see:

24a Barton DHR. Jaszberenyi JC. Theodorakis EA. J. Am. Chem. Soc.  1992,  114:  5904 

24b Barton DHR. Jaszberenyi JS. Theodorakis EA. Reibenspies JH.
J. Am. Chem. Soc.  1993,  115:  8050 

For recent reports on arenediazonium salts as radical scavengers, see:

25a Heinrich MR. Blank O. Wölfel S. Org. Lett.  2006,  8:  3323 

25b Blank O. Heinrich MR. Eur. J. Org. Chem.  2006,  4331 

25c Heinrich MR. Blank O. Wetzel A. Synlett  2006,  3352 

25d Heinrich MR. Blank O. Wetzel A. J. Org. Chem.  2007,  72:  476 

25e Blank O. Wetzel A. Ullrich D. Heinrich MR. Eur. J. Org. Chem.  2008,  3179 

26 Criegee R. Houben-Weyl   Vol. VIII:  Georg Thieme Verlag; Stuttgart: 1968.  p.1-74  

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 

27b Blank O. Raschke N. Heinrich MR. Tetrahedron Lett.  2010,  51:  1758 

28

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

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 

29b Walling C. Acc. Chem. Res.  1975,  8:  125 

29c Schreiber SL. J. Am. Chem. Soc.  1980,  102:  6163 

29d Schreiber SL. Hulin B. Liew W.-F. Tetrahedron  1986,  42:  2945 

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 

30b Hartung J. Gottwald T. Spehar K. Synthesis  2002,  1469 

31a Francisco CG. González CC. Kennedy AR. Paz NR. Suárez E. Chem. Eur. J.  2008,  14:  6704 

31b Alonso-Cruz CR. Kennedy AR. Rodriguez MS. Suárez E. Tetrahedron Lett.  2007,  48:  7207 

31c Dichtl A. Seyfried M. Schoening K.-U. Synlett  2008,  1877 

For review articles on arenediazonium salts as sources for aryl radicals, see:

32a Galli C. Chem. Rev.  1988,  88:  765 

32b Heinrich MR. Chem. Eur. J.  2009,  15:  820 

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 

33b Hawkins EGE. J. Chem. Soc.  1955,  3463 

33c Kharasch MS. Nudenberg W. J. Org. Chem.  1954,  19:  1921 

33d Braunwarth JB. Crosby GW. J. Org. Chem.  1962,  27:  2064 

33e De La Mare HE. Kochi JK. Rust FF. J. Am. Chem. Soc.  1963,  85:  1437 

For recent reports on bond strengths and radical stability, see:

34a Zipse H. Top. Curr. Chem.  2006,  263:  163 

34b Zavitsas A. J. Org. Chem.  2008,  73:  9022 

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 

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 

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 

37b Criegee R. Schnorrenberg W. Becke J. Justus Liebigs Ann. Chem.  1949,  565:  7 

37c Karasch MS. Sosnovsky G. J. Org. Chem.  1958,  23:  1322 

37d Brown N. Hartig MJ. Roedel MJ. Anderson AW. Schweitzer CE. J. Am. Chem. Soc.  1955,  77:  1756 

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 

39

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

40 Röder E. Krauß H. Liebigs Ann. Chem.  1992,  177 

41 Heinrich MR. Blank O. Ullrich D. Kirschstein M.
J. Org. Chem.  2007,  72:  9609 

42 Elofson RM. Gadallah FF. J. Org. Chem.  1971,  36:  1769 

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 

43b Khaimov IN. Trudy Tadzhik. Sel’skokhoz. Inst.  1958,  1:  33 

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.

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 

46 A mixture was obtained when using classical Beckmann conditions: Schäffler A. Ziegenbein W. Chem. Ber.  1955,  88:  1374 

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.

49 de Vleeschouwer F. van Speybroeck V. Waroquier M. Geerlings P. de Proft F. Org. Lett.  2007,  9:  2721 

50a

See ref. 25d.

50b Haag BA. Zhang Z. Li J. Knochel P. Angew. Chem. Int. Ed.  2010,  49:  9513 

50c Rossiter S. Folkes LK. Wardman P. Bioorg. Med. Chem. Lett.  2002,  12:  2523 

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 

52a Molina CL. Chow CP. Shea KJ. J. Org. Chem.  2007,  72:  6816 

52b Rautenstrauch V. Delay F. Angew. Chem. Int. Ed.  1980,  19:  726 

52c Matsuyama H. Itoh N. Matsumoto A. Ohira N. Hara K. Yoshida M. Iyoda M. J. Chem. Soc., Perkin Trans. 1  2001,  2924 

52d Fernández R. Ferrete A. Llera JM. Magriz A. Martín-Zamora E. Díez E. Lassaletta JM. Chem. Eur. J.  2004,  10:  737 

52e Friestad GK. Qin J. J. Am. Chem. Soc.  2001,  123:  9922 

53

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

54a Gruner M. Pfeifer D. Becker HGO. Radeglia R. Epperlein J. J. Prakt. Chem.  1985,  327:  63 

54b Bahr JL. Yang J. Kosynkin DV. Bronikowski MJ. Smalley RE. Tour JM. J. Am. Chem. Soc.  2001,  123:  6536 

55 Burnell DJ. Wu Y. Can. J. Chem.  1990,  68:  804 

56 Haynes RK. King GR. Vonwiller SC. J. Org. Chem.  1994,  59:  4743 

57a Golding BT. Bleasdale C. McGinnis J. Müller S. Rees HT. Rees NH. Farmer PB. Watson WP. Tetrahedron  1997,  53:  4063 

57b Snyder JK. Stock LM. J. Org. Chem.  1980,  45:  886 

58a Takemiya A. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  14800 

58b Schmidt AM. Eilbracht P. Org. Biomol. Chem.  2005,  3:  2333 

59 Bullock MW. Fox SW. J. Am. Chem. Soc.  1951,  73:  5155 

60 Ramalingan C. Park Y.-T. Synthesis  2008,  1351