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RESEARCH ARTICLE
Contents Vol 67(3)

Formation and HERON Reactivity of Cyclic N,N-Dialkoxyamides

Stephen A. Glover A B , Adam A. Rosser A , Avat (Arman) Taherpour A and Ben W. Greatrex A
+ 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 67(3) 507-520 https://doi.org/10.1071/CH13557
Submitted: 15 October 2013  Accepted: 27 November 2013   Published: 30 January 2014

Abstract

Cyclic N,N-dialkoxyamides have been made, for the first time, by hypervalent iodine oxidation of β- and γ-hydroxyhydroxamic esters 17, 19, and 21. The fused γ-lactam products, N-butoxy- and N-benzyloxybenzisoxazolones (22a and 22b), are stable while alicyclic γ-lactam and δ-lactam products, 24 and 25, although observable by NMR spectroscopy and ESI-MS are unstable at room temperature, undergoing HERON reactions. The γ-lactam 24 undergoes exclusive ring opening to give a butyl ester-functionalised alkoxynitrene 28. The δ-lactam 25, instead, undergoes a HERON ring contraction to give butyrolactone (27). The structures of model γ- and δ-lactams 6, 7, and 8 have been determined at the B3LYP/6-31G(d) level of theory and the γ-lactams are much more twisted than the acyclic N,N-dimethoxyacetamide (5) resulting in a computed amidicity for 6 of only 25 % that of N,N-dimethylacetamide (3). The HERON reactions of N,N-dimethoxyacetamide (5) and alicyclic models 6 and 8 have been modelled computationally. The facile ring opening of 6 (EA = 113 kJ mol–1) and ring contraction of 8 (EA = 145 kJ mol–1) are predicted well, when compared with the HERON rearrangement of 5 (EA = 178 kJ mol–1).


References

[1]  K. M. Digianantonio, S. A. Glover, J. P. Johns, A. A. Rosser, Org. Biomol. Chem. 2011, 9, 4116.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXmtFyhtLY%3D&md5=897643d2c0c772f63d94f685ae669835CAS | 21499599PubMed |

[2]  S. A. Glover, J. M. White, A. A. Rosser, K. M. Digianantonio, J. Org. Chem. 2011, 76, 9757.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtlCiurjK&md5=784e577331fd74430fb16cd67d470a3fCAS | 22017195PubMed |

[3]  A. M. Bonin, S. A. Glover, G. P. Hammond, J. Chem. Soc., Perkin Trans. 2 1994, 1173.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXktlCmt7o%3D&md5=ef001634806637087eef249842864d0eCAS |

[4]  J. M. Buccigross, S. A. Glover, G. P. Hammond, Aust. J. Chem. 1995, 48, 353.
         | 1:CAS:528:DyaK2MXktFGjs7o%3D&md5=34521f9c4b78e60a12dbd2f8f73d627fCAS |

[5]  A. Rauk, S. A. Glover, J. Org. Chem. 1996, 61, 2337.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28Xhs1Cgs7o%3D&md5=3f8e94e5f4dcf5161d0191f9d379c464CAS |

[6]  S. A. Glover, Tetrahedron 1998, 54, 7229.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXjvFWktL4%3D&md5=8b145d854086ce4480b7a7f84e363d4fCAS |

[7]  S. A. Glover, G. P. Hammond, A. M. Bonin, J. Org. Chem. 1998, 63, 9684.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXnsFKls7s%3D&md5=1fbc864b27f056b835bba5e7e2c029c9CAS |

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

[9]  S. A. Glover, G. Mo, A. Rauk, Tetrahedron 1999, 55, 3413.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXhslyhsro%3D&md5=87785c3da65ee6e96bac100581b931dcCAS |

[10]  S. A. Glover, A. Rauk, J. Org. Chem. 1999, 64, 2340.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXhs1yit7g%3D&md5=8bcb59af8249bfe1fb00b566c9677c62CAS |

[11]  S. A. Glover, G. Mo, A. Rauk, D. Tucker, P. Turner, J. Chem. Soc., Perkin Trans. 2 1999, 2053.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXmtFKltrw%3D&md5=eb0985e03e7429e15c000fa78488205cCAS |

[12]  G. Mo, Properties and Reactions of Anomeric Amides 1999, Ph.D. thesis, University of New England, Armidale.

[13]  S. A. Glover, G. Mo, J. Chem. Soc., Perkin Trans. 2 2002, 1728.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XnsVeitL4%3D&md5=4242898a72c7ef64eb5d8eac8ff67bc4CAS |

[14]  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 | 1:CAS:528:DC%2BD28XlvVarsQ%3D%3D&md5=21f7247064e31a76bfdec1a1cf57afcaCAS |

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

[16]  S. A. Glover, in Advances in Physical Organic Chemistry (Ed. J. Richard) 2008, Vol. 42, pp. 35–123 (Elsevier: London).

[17]  S. A. Glover, in The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids, Part 2 (Eds Z. Rappoport, J. F. Liebman) 2009, pp. 839–923 (Wiley: Chichester).

[18]  J. P. Johns, A. van Losenoord, C. Mary, P. Garcia, D. S. Pankhurst, A. A. Rosser, S. A. Glover, Aust. J. Chem. 2010, 63, 1717.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsFaqsbvF&md5=930e933e8a897c822b34255ade4d0711CAS |

[19]  S. A. Glover, M. Adams, Aust. J. Chem. 2011, 64, 443.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXkvVCrs7s%3D&md5=6a20f52be4472bd33be8a57799f07530CAS |

[20]  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 | 1:CAS:528:DC%2BD2cXjtVGnuw%3D%3D&md5=3064aa57b37de4f29cc74c3e7a30a3a1CAS |

[21]  V. G. Shtamburg, A. V. Tsygankov, E. A. Klots, R. G. Kostyanovsky, Mendeleev Commun. 2004, 14, 208.
         | Crossref | GoogleScholarGoogle Scholar |

[22]  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 |

[23]  V. G. Shtamburg, O. V. Shishkin, R. I. Zubatyuk, S. V. Kravchenko, A. V. Tsygankov, A. V. Mazepa, E. A. Klots, R. G. Kostyanovsky, Mendeleev Commun. 2006, 16, 323.
         | Crossref | GoogleScholarGoogle Scholar |

[24]  V. G. Shtamburg, O. V. Shishkin, R. I. Zubatyuk, S. V. Kravchenko, A. V. Tsygankov, V. V. Shtamburg, V. B. Distanov, R. G. Kostyanovsky, Mendeleev Commun. 2007, 17, 178.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtVelsrzK&md5=c23fd23fe4ceb7140db03445964f22c2CAS |

[25]  V. G. Shtamburg, A. V. Tsygankov, O. V. Shishkin, R. I. Zubatyuk, V. V. Shtamburg, M. V. Gerasimenko, A. V. Mazepa, R. G. Kostyanovsky, Mendeleev Commun. 2012, 22, 92.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xls1Wlt7s%3D&md5=a86df4ae9736acb076a8ff4001fefd06CAS |

[26]  V. G. Shtamburg, A. T. Tsygankov, O. V. Shishkin, R. I. Zubatyuk, B. V. Uspensky, V. V. Shtamburg, A. V. Mazepa, R. G. Kostyanovsky, Mendeleev Commun. 2012, 22, 164.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XnvVylsrk%3D&md5=72b2787b3348381ab9f0f67523ba5b7fCAS |

[27]  S. A. Glover, A. A. Rosser, J. Org. Chem. 2012, 77, 5492.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XnslGqs78%3D&md5=46b5fb7554e7ec6a6e11280500bca52bCAS | 22646836PubMed |

[28]  Z. Mucsi, A. Tsai, M. Szori, G. A. Chass, B. Viscolcz, I. G. Csizmadia, J. Phys. Chem. A 2007, 111, 13245.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtlGis73L&md5=0699eb199c1ff0822aced9fe66888153CAS | 18041826PubMed |

[29]  J. M. Buccigross, S. A. Glover, J. Chem. Soc., Perkin Trans. 2 1995, 595.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXktlCmsLw%3D&md5=faa86a4619abce2efa9a06e123cfb2fdCAS |

[30]  F. K. Winkler, J. D. Dunitz, J. Mol. Biol. 1971, 59, 169.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3MXkvFahtrY%3D&md5=fc2b46063ffd26e1db36071fdc8f9038CAS | 5283751PubMed |

[31]  J. D. Dunitz, X-Ray Analysis and Structure of Organic Molecules 1979 (Cornell University Press: London).

[32]  A. Greenberg, in The Amide Linkage. Structural Significance in Chemistry, Biochemistry and Materials Science (Eds A. Greenberg, C. M. Breneman, J. F. Liebman) 2003, pp. 47–83 (John Wiley & Sons, Inc.: New York, NY).

[33]  A. Greenberg, D. T. Moore, T. D. DuBois, J. Am. Chem. Soc. 1996, 118, 8658.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28XltFeks78%3D&md5=62e677af118e1f8769335c9a6de8f78fCAS |

[34]  A. Greenberg, C. A. Venanzi, J. Am. Chem. Soc. 1993, 115, 6951.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3sXlvVSgsrg%3D&md5=bcc348892fb4151533c417ae787a5d95CAS |

[35]  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 | 1:CAS:528:DC%2BD3MXjsVGju78%3D&md5=a51d1b19aa5a00661a54ce3459f5e360CAS | 11389628PubMed |

[36]  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 | 1:CAS:528:DC%2BD28Xps1aksLo%3D&md5=882b6a26bf13b60698aaa9ee1e6928e1CAS | 17017794PubMed |

[37]  M. S. Platz, in Reactive Intermediate Chemistry (Eds R. A. Moss, M. S. Platz, M. Jones) 2004, pp. 501–559 (Wiley: Hoboken, NJ).

[38]  M. I. Page, Acc. Chem. Res. 1984, 17, 144.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2cXhtlWrt7s%3D&md5=c8dbe1977fe1cf60474cd358426a90c5CAS |

[39]  M. I. Page, Adv. Phys. Org. Chem. 1987, 23, 165.
         | 1:CAS:528:DyaL1cXktFKnsb0%3D&md5=fdd97c44d40eb4da1452684236781ad0CAS |

[40]  C. R. Hauser, W. B. Renfrow Jr, 1943, Organic Synthesis Collective, Vol. II, p. 67 (John Wiley & Sons, Inc.: New York, NY).

[41]  J. H. Cooley, W. D. Bills, J. R. Throckmorton, J. Org. Chem. 1960, 25, 1734.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF3MXhtlajtw%3D%3D&md5=d3ab4fe52e94ea4200bcb42816932d92CAS |

[42]  J. J. Campbell, S. A. Glover, C. A. Rowbottom, Tetrahedron Lett. 1990, 31, 5377.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXitlajsQ%3D%3D&md5=c58a2c466a2cb49d1ce930e53549c314CAS |

[43]  J. J. Campbell, S. A. Glover, G. P. Hammond, C. A. Rowbottom, J. Chem. Soc., Perkin Trans. 2 1991, 2067.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XhtVGgtbw%3D&md5=05cfd21576fd26a0ac93875148b58cd1CAS |

[44]  Spartan10 for Macintosh 1.1.0 2010 (Wavefunction Inc.: Irvine, CA).

[45]  M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ocherski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenburg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. C. Ortiz, Q. A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, Revision E.01 2005 (Gaussian, Inc.: Wallingford, CT).

[46]  R. R. Vakhidov, R. N. Shakhmaev, G. Y. Ishmuratov, V. V. Zorin, Russ. J. Electrochem. 2000, 36, 771.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXitVenug%3D%3D&md5=bf607ef1163d347c0a5f3702b7f24ce4CAS |

[47]  M. J. Mintz, C. Walling, Org. Synth. 1963, 49, 9.