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Contents Vol 63(12)

Thermal Decomposition of N-Acyloxy-N-alkoxyamides – a New HERON Reaction

Jennifer P. Johns A , Arjan van Losenoord A , Clément Mary A , Pierre Garcia A , Damian S. Pankhurst A , Adam A. Rosser A and Stephen A. Glover A B
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, School of Science and Technology, University of New England, Armidale, NSW 2351, Australia.

B Corresponding author. Email: sglover@une.edu.au

Australian Journal of Chemistry 63(12) 1717-1729 https://doi.org/10.1071/CH10350
Submitted: 23 September 2010  Accepted: 22 October 2010   Published: 6 December 2010

Abstract

The HERON reaction has been observed in the thermal decompositions of N-acyloxy-N-alkoxyamides 1b, members of the class of anomeric amides. The N,N-bisoxo-substitution results in reduced amide resonance and this, combined with an nO–σ*NOAcyl anomeric destabilization of the N–OAcyl bond, results in their intramolecular rearrangement to anhydrides 42 and alkoxynitrenes 43 in competition with homolysis of the N–OAcyl bond to alkoxyamidyls 51. The primary HERON product alkoxynitrenes are scavenged by oxygen, giving a nitrate ester, in competition with a rearrangement to nitriles and dimerization to hyponitrites, leading, under the conditions, to alcohols and aldehydes. Persistent alkoxyamidyls most likely form a 1,3-diradical in a solvent-cage reaction, which cyclizes to 3,5-disubstituted-(5H)-1,4,2-dioxazoles 47. Substituent effects support this competition reaction.


References

[1]  S. A. Glover, Tetrahedron 1998, 54, 7229.
         | Crossref | GoogleScholarGoogle Scholar |

[2]  S. A. Glover, in The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids, Part 2 2009, p. 839 (Eds Z. Rappoport, J. F. Liebman) (Wiley: Chichester).

[3]  S. A. Glover, in Advances in Physical Organic Chemistry 2008, Vol. 42, p. 35 (Ed. J. Richard) (Elsevier: London).

[4]  S. A. Glover, G. Mo, A. Rauk, Tetrahedron 1999, 55, 3413.
         | Crossref | GoogleScholarGoogle Scholar |

[5]  O. V. Shishkin, R. I. Zubatyuk, V. G. Shtamburg, A. V. Tsygankov, E. A. Klots, A. V. Mazepa, R. G. Kostyanovsky, Mendeleev Commun. 2006, 16, 222.
         | Crossref | GoogleScholarGoogle Scholar |

[6]  V. G. Shtamburg, E. A. Klots, A. P. Pleshkova, V. I. Avramenko, S. P. Ivonin, A. V. Tsygankov, R. G. Kostyanovsky, Russ. Chem. Bull. 2003, 52, 2251.
         | Crossref | GoogleScholarGoogle Scholar |

[7]  V. G. Shtamburg, V. F. Rudchenko, S. S. Nasibov, I. I. Chervin, R. G. Kostyanovskii, Izv. Akad. Nauk SSSR [Khim] 1981, 449.

[8]  P. Deslongchamps, Stereoelectronic Effects in Organic Chemistry 1984, Vol. 1, p. 4 (Pergamon Press: Oxford).

[9]  E. L. Eliel, S. H. Wilen, L. N. Mander, Stereochemistry of Organic Compounds 1994, p. 753 (John Wiley & Sons, Inc.: New York, NY).

[10]  A. Rauk, Orbital Interaction Theory of Organic Chemistry 1994, p. 102 (John Wiley & Sons, Inc.: New York, NY).

[11]  S. A. Glover, A. Goosen, C. W. McCleland, J. L. Schoonraad, J. Chem. Soc., Perkin Trans. 1 1984, 2255.
         | Crossref | GoogleScholarGoogle Scholar |

[12]  S. A. Glover, A. Goosen, C. W. McCleland, J. L. Schoonraad, Tetrahedron 1987, 43, 2577.
         | Crossref | GoogleScholarGoogle Scholar |

[13]  S. A. Glover, A. P. Scott, Tetrahedron 1989, 45, 1763.
         | Crossref | GoogleScholarGoogle Scholar |

[14]  M. Kawase, T. Kitamura, Y. Kikugawa, J. Org. Chem. 1989, 54, 3394.
         | Crossref | GoogleScholarGoogle Scholar |

[15]  Y. Kikugawa, M. Kawase, J. Am. Chem. Soc. 1984, 106, 5728.
         | Crossref | GoogleScholarGoogle Scholar |

[16]  Y. Kikugawa, M. Shimada, Chem. Lett. 1987, 16, 1771.
         | Crossref | GoogleScholarGoogle Scholar |

[17]  D. Schroeder, F. Grandinetti, J. Hrusak, H. Schwarz, J. Phys. Chem. 1992, 96, 4841.
         | Crossref | GoogleScholarGoogle Scholar |

[18]  K. L. Cavanagh, S. A. Glover, H. L. Price, R. R. Schumacher, Aust. J. Chem. 2009, 62, 700.
         | Crossref | GoogleScholarGoogle Scholar |

[19]  S. A. Glover, G. Mo, J. Chem. Soc., Perkin Trans. 2 2002, 1728.
         | Crossref | GoogleScholarGoogle Scholar |

[20]  S. A. Glover, Arkivoc 2001, Part xii, Issue in Honour of O.S.Tee, ms. OT-308C, 143.

[21]  J. J. Campbell, S. A. Glover, J. Chem. Res. (M) 1999, 8, 2075.

[22]  J. J. Campbell, S. A. Glover, J. Chem. Res. (S) 1999, 8, 474.
         | Crossref | GoogleScholarGoogle Scholar |

[23]  S. A. Glover, A. Rauk, J. M. Buccigross, J. J. Campbell, G. P. Hammond, G. Mo, L. E. Andrews, A.-M. E. Gillson, Can. J. Chem. 2005, 83, 1492.
         | Crossref | GoogleScholarGoogle Scholar |

[24]  J. M. Buccigross, S. A. Glover, J. Chem. Soc., Perkin Trans. 2 1995, 595.
         | Crossref | GoogleScholarGoogle Scholar |

[25]  J. M. Buccigross, S. A. Glover, G. P. Hammond, Aust. J. Chem. 1995, 48, 353.

[26]  S. A. Glover, in Merck Index, Organic Name Reactions ONR-43 2006 (Ed. M. J. O’Neil) (Merck & Co., Inc.: Whitehouse Station, NJ).

[27]  R. G. Gerdes, S. A. Glover, J. F. Ten Have, C. A. Rowbottom, Tetrahedron Lett. 1989, 30, 2649.
         | Crossref | GoogleScholarGoogle Scholar |

[28]  J. J. Campbell, S. A. Glover, C. A. Rowbottom, Tetrahedron Lett. 1990, 31, 5377.
         | Crossref | GoogleScholarGoogle Scholar |

[29]  J. J. Campbell, S. A. Glover, G. P. Hammond, C. A. Rowbottom, J. Chem. Soc., Perkin Trans. 2 1991, 2067.
         | Crossref | GoogleScholarGoogle Scholar |

[30]  J. J. Campbell, S. A. Glover, J. Chem. Soc., Perkin Trans. 2 1992, 1661.
         | Crossref | GoogleScholarGoogle Scholar |

[31]  A. M. Bonin, S. A. Glover, G. P. Hammond, J. Chem. Soc., Perkin Trans. 2 1994, 1173.
         | Crossref | GoogleScholarGoogle Scholar |

[32]  S. A. Glover, G. P. Hammond, A. M. Bonin, J. Org. Chem. 1998, 63, 9684.
         | Crossref | GoogleScholarGoogle Scholar |

[33]  T. M. Banks, A. M. Bonin, S. A. Glover, A. S. Prakash, Org. Biomol. Chem. 2003, 1, 2238.
         | Crossref | GoogleScholarGoogle Scholar | 12945693PubMed |

[34]  A.-M. E. Gillson, S. A. Glover, D. J. Tucker, P. Turner, Org. Biomol. Chem. 2003, 1, 3430.
         | Crossref | GoogleScholarGoogle Scholar | 14584807PubMed |

[35]  L. E. Andrews, T. M. Banks, A. M. Bonin, S. F. Clay, A.-M. E. Gillson, S. A. Glover, Aust. J. Chem. 2004, 57, 377.
         | Crossref | GoogleScholarGoogle Scholar |

[36]  L. E. Andrews, A. M. Bonin, L. Fransson, A.-M. E. Gillson, S. A. Glover, Mutat. Res. 2006, 605, 51.
         | 16698311PubMed |

[37]  S. A. Glover, A. Rauk, J. Chem. Soc., Perkin Trans. 2 2002, 1740.
         | Crossref | GoogleScholarGoogle Scholar |

[38]  M. V. De Almeida, D. H. R. Barton, I. Bytheway, J. A. Ferriera, M. B. Hall, W. Liu, D. K. Taylor, L. Thomson, J. Am. Chem. Soc. 1995, 117, 4870.
         | Crossref | GoogleScholarGoogle Scholar |

[39]  L. M. Thomson, M. B. Hall, J. Phys. Chem. A 2000, 104, 6247.
         | Crossref | GoogleScholarGoogle Scholar |

[40]  A. Selva, A. Citterio, E. Pella, R. Tonani, Org. Mass Spectrom. 1974, 9, 1017.
         | Crossref | GoogleScholarGoogle Scholar |

[41]  M. S. Platz, in Reactive Intermediate Chemistry 2004, p. 501 (Eds R. A. Moss, M. S. Platz, M. Jones) (Wiley Interscience: Hoboken, NJ).

[42]  A. Srinivasan, N. Kebede, J. E. Saavedra, A. V. Nikolaitchik, D. A. Brady, E. Yourd, K. M. Davies, L. K. Keefer, J. P. Toscano, J. Am. Chem. Soc. 2001, 123, 5465.
         | Crossref | GoogleScholarGoogle Scholar | 11389628PubMed |

[43]  W. A. Wasylenko, N. Kebede, B. M. Showalter, N. Matsunaga, A. P. Miceli, Y. Liu, L. R. Ryzhkov, C. M. Hadad, J. P. Toscano, J. Am. Chem. Soc. 2006, 128, 13142.
         | Crossref | GoogleScholarGoogle Scholar | 17017794PubMed |

[44]  R. O. C. Norman, R. Purchase, C. B. Thomas, J. Chem. Soc., Perkin Trans. 1 1972, 1701.
         | Crossref | GoogleScholarGoogle Scholar |

[45]  E. M. Y. Quinga, G. D. Mendenhall, J. Org. Chem. 1985, 50, 2836.
         | Crossref | GoogleScholarGoogle Scholar |

[46]  S. R. Sandler, W. Karo, Organic Functional Group Preparations 1972, Vol. III (Academic Press: New York, NY).

[47]  C. D. Hurd, M. F. Dull, J. Am. Chem. Soc. 1932, 54, 3427.
         | Crossref | GoogleScholarGoogle Scholar |

[48]  K. U. Ingold, J. C. Walton, in Landolt Börnstein II 17c 1987 (Springer Verlag: Berlin).

[49]  S. A. Glover, A. Goosen, C. W. McCleland, J. L. Schoonraad, J. Chem. Soc., Perkin Trans. 2 1986, 645.
         | Crossref | GoogleScholarGoogle Scholar |

[50]  A. R. Forrester, E. M. Johansson, R. H. Thomson, J. Chem. Soc., Perkin Trans. 1 1979, 1112.
         | Crossref | GoogleScholarGoogle Scholar |

[51]  A. R. Forrester, H. Irikawa, J. Chem. Soc. Chem. Commun. 1981, 253.
         | Crossref | GoogleScholarGoogle Scholar |

[52]  T. Koenig, J. A. Hoobler, W. R. Mabey, J. Am. Chem. Soc. 1972, 94, 2514.
         | Crossref | GoogleScholarGoogle Scholar |

[53]  T. Koenig, J. A. Hoobler, C. E. Klopfenstein, G. Heddon, F. Sunderman, B. R. Russell, J. Am. Chem. Soc. 1974, 96, 4573.
         | Crossref | GoogleScholarGoogle Scholar |

[54]  J. H. Cooley, M. W. Mosher, M. A. Khan, J. Am. Chem. Soc. 1968, 90, 1867.
         | Crossref | GoogleScholarGoogle Scholar |

[55]  K. M. Koshy, R. E. Robertson, Can. J. Chem. 1974, 52, 2485.
         | Crossref | GoogleScholarGoogle Scholar |

[56]  C. H. Hauser, D. S. Hoffenberg, J. Am. Chem. Soc. 1955, 20, 1491.

[57]  G. D. Mendenhall, J. Am. Chem. Soc. 1974, 96, 5000.
         | Crossref | GoogleScholarGoogle Scholar |

[58]  C. A. Ogle, S. W. Martin, M. P. Dziobak, M. W. Urban, G. D. Mendenhall, J. Org. Chem. 1983, 48, 3728.
         | Crossref | GoogleScholarGoogle Scholar |