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You are here: Home > Journals > CH > CH16683
RESEARCH ARTICLE
Contents Vol 70(4)

Development of the HERON Reaction: A Historical Account

Stephen A. Glover A
+ Author Affiliations
- Author Affiliations

A Chemistry, School of Science and Technology, University of New England, Armidale, NSW 2351, Australia. Email: sglover@une.edu.au

Australian Journal of Chemistry 70(4) 344-361 https://doi.org/10.1071/CH16683
Submitted: 3 December 2016  Accepted: 18 January 2017   Published: 22 February 2017

Abstract

This account describes the discovery and development of the HERON reaction, a reaction with special connection to the Heron Island Conferences on Reactive Intermediates and Unusual Molecules. This modern ‘named’ reaction describes an unusual rearrangement of bisheteroatom-substituted amides RCON(X)(Y) whereby the more electron deficient group, X, migrates from nitrogen to the carbonyl carbon giving an acyl derivative, RC(O)X, and Y-stabilised nitrenes. In it, the origins, mechanistic elucidation, and theoretical validation are described in more or less chronological order. Along that time line we introduce the concepts of ‘anomeric amides’, ‘amidicity’ in anomeric amides, and their role in the HERON reaction. All known versions of the reaction that have since been discovered are outlined and a basic understanding of the relative roles of reduced resonance and the anomeric driving force, both functions of the heteroatom substituents at the amide nitrogen, are quantified.


References

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

[2]  J. M. Buccigross, S. A. Glover, J. Chem. Soc., Perkin Trans. 2 1995, 595.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXktlCmsLw%3D&md5=d00a330a00451e5575849db3b6ac0f18CAS |

[3]  S. A. Glover, in Merck Index, Organic Name Reactions ONR-48 (Ed. M. J. O’Neil) 2001 (Merck & Co., Inc.: Whitehouse Station, NJ).

[4]  R. G. Gerdes, S. A. Glover, J. F. Ten Have, C. A. Rowbottom, Tetrahedron Lett. 1989, 30, 2649.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3cXjsFerug%3D%3D&md5=14318e4ce47e53a42989bd6553ea873cCAS |

[5]  J. J. Campbell, S. A. Glover, C. A. Rowbottom, Tetrahedron Lett. 1990, 31, 5377.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXitlajsQ%3D%3D&md5=afdbf4380c3683c4ca2018fb57b42248CAS |

[6]  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=a79e8bd06529758f68eea8499b0a9750CAS |

[7]  T. M. Banks, A. M. Bonin, S. A. Glover, A. S. Prakash, Org. Biomol. Chem. 2003, 1, 2238.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXkvFWqsrc%3D&md5=2496f9ef360d0c1c8be9aad2d5a52e13CAS |

[8]  M. Famulok, G. Boche, Angew. Chem. Int. Ed. Engl. 1989, 28, 468.
         | Crossref | GoogleScholarGoogle Scholar |

[9]  F. Bosold, G. Boche, Angew. Chem. Int. Ed. Engl. 1990, 29, 63.
         | Crossref | GoogleScholarGoogle Scholar |

[10]  R. Ulbrich, M. Famulok, F. Bosold, G. Boche, Tetrahedron Lett. 1990, 31, 1689.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3cXlsFamtLk%3D&md5=f1587eca840601eb12594dce9d5dc5dcCAS |

[11]  J. S. Helmick, K. A. Martin, J. L. Heinrich, M. Novak, J. Am. Chem. Soc. 1991, 113, 3459.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXitVKhtrc%3D&md5=f5ea922aa237602b546808921dff1ae2CAS |

[12]  M. Novak, K. S. Rangappa, J. Org. Chem. 1992, 57, 1285.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XhtVGgtL8%3D&md5=527744df04a9e8dbb718ca3bb37dbff4CAS |

[13]  J. J. Campbell, S. A. Glover, J. Chem. Soc., Perkin Trans. 2 1992, 1661.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3sXitF2jug%3D%3D&md5=aaf16fc3ae231713ef8b2e16eb997e17CAS |

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

[15]  J. J. Campbell, S. A. Glover, J. Chem. Res., Miniprint 1999, 8, 2075.

[16]  W. D. Hinsberg, P. B. Dervan, J. Am. Chem. Soc. 1608, 1978, 5.

[17]  W. D. Hinsberg, P. B. Dervan, J. Am. Chem. Soc. 1979, 101, 6142.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1MXlvFamtLw%3D&md5=2ae4c519523c6043ead25f41b9b42b7dCAS |

[18]  P. G. Schultz, P. B. Dervan, J. Am. Chem. Soc. 1980, 102, 878.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3cXhvVSms7o%3D&md5=157eeeba80d54577de1d05e1ec7c0deaCAS |

[19]  P. G. Schultz, P. B. Dervan, J. Am. Chem. Soc. 1981, 103, 1563.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3MXktFGrtrY%3D&md5=f0ed45d7c1a5261edaba1769de304680CAS |

[20]  P. B. Dervan, M. E. Squillacote, P. M. Lahti, A. P. Sylwester, J. D. Roberts, J. Am. Chem. Soc. 1981, 103, 1120.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3MXht12rtb0%3D&md5=dbe92c05672e03927d8ed0031a113009CAS |

[21]  P. G. Schultz, P. B. Dervan, J. Am. Chem. Soc. 1982, 104, 6660.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL38XlvFOmtLo%3D&md5=5bf1011415b9bee6ef69f8284c2a025dCAS |

[22]  W. D. Hinsberg, P. G. Schultz, P. B. Dervan, J. Am. Chem. Soc. 1982, 104, 766.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL38XmvVWgsw%3D%3D&md5=1ef765878c7ff39a976632b7a46b53b0CAS |

[23]  S. A. Glover, A. Goosen, H. A. H. Laue, J. Chem. Soc., Perkin Trans. 1 1973, 1647.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3sXltlKktrs%3D&md5=728e4e4a34f770766dc74c6795a324dbCAS |

[24]  S. A. Glover, A. Goosen, J. Chem. Soc., Perkin Trans. 1 1974, 2353.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2MXht1Gjs7w%3D&md5=719f58fa41a9a9dd3a42d09ab8bffaafCAS |

[25]  S. A. Glover, A. Goosen, C. W. McCleland, J. L. Schoonraad, Tetrahedron 1987, 43, 2577.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXlsFaisg%3D%3D&md5=b462221d8a5141705a3d08d96ba1c15eCAS |

[26]  J. H. Cooley, D. M. Stone, H. Oguri, J. Org. Chem. 1977, 42, 3096.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2sXltFOnsrk%3D&md5=2df4adb75b8741d62df706d4878af777CAS |

[27]  J. H. Cooley, M. W. Mosher, M. A. Khan, J. Am. Chem. Soc. 1968, 90, 1867.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF1cXhtFCjsLg%3D&md5=109e6a58154f756f193fbf411a92e793CAS |

[28]  J. M. Buccigross, S. A. Glover, G. P. Hammond, Aust. J. Chem. 1995, 48, 353.
         | 1:CAS:528:DyaK2MXktFGjs7o%3D&md5=1746bce84cb723bb5df375a18db9368bCAS |

[29]  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 | 1:CAS:528:DyaK2MXlt1SrtLg%3D&md5=be71980c4163a4aa0cde9089e0c177d0CAS |

[30]  N. Zhang, R. Yang, D. Zhang-Negrerie, Y. Du, K. Zhao, J. Org. Chem. 2013, 78, 8705.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXht1Chs7bF&md5=939123533a439d3d6095b4839d2ca1c4CAS |

[31]  A.-M. E. Gillson, S. A. Glover, D. J. Tucker, P. Turner, Org. Biomol. Chem. 2003, 1, 3430.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXnsFGku7s%3D&md5=7f121e43bfb3bf952847712906fb0e75CAS |

[32]  A. Rauk, S. A. Glover, J. Org. Chem. 1996, 61, 2337.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28Xhs1Cgs7o%3D&md5=5fe896d9001811cbb88a6f3f2c4846ceCAS |

[33]  S. A. Glover, A. Rauk, J. Org. Chem. 1999, 64, 2340.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXhs1yit7g%3D&md5=9a85e8d27416e1163e708bb87b1c15a4CAS |

[34]  H. A. Bent, Chem. Rev. 1961, 61, 275.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF3MXptVyksQ%3D%3D&md5=6adcae2c04058358884010bb7d31cb24CAS |

[35]  I. V. Alabugin, S. Bresch, M. Manoharan, J. Phys. Chem. A 2014, 118, 3663.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXmvFCjt7w%3D&md5=6d5c66a5da4065db8a40dff2bb3156bcCAS |

[36]  I. V. Alabugin, S. Bresch, G. dos Passos Gomez, J. Phys. Org. Chem. 2015, 28, 147.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhvFKksr%2FO&md5=f6a4f73cfe5c767bb9b7fcbe9b453f01CAS |

[37]  F. K. Winkler, J. D. Dunitz, J. Mol. Biol. 1971, 59, 169.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3MXkvFahtrY%3D&md5=979c6475184f0eebfb5885588fbd1c68CAS |

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

[39]  S. A. Glover, Tetrahedron 1998, 54, 7229.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXjvFWktL4%3D&md5=7a5f36aae9fa8752f1212b8da6398258CAS |

[40]  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).

[41]  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=cf6253f76728e29a04f88b4541a0cdb7CAS |

[42]  S. A. Glover, G. Mo, A. Rauk, Tetrahedron 1999, 55, 3413.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXhslyhsro%3D&md5=3c1d528235c8cbe9fb4dd05683784c6bCAS |

[43]  L. M. Thomson, M. B. Hall, J. Phys. Chem. A 2000, 104, 6247.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXjvVCktLc%3D&md5=fbc0a4ff8fc07ba3dac5b66ac1e986dbCAS |

[44]  Merck Index - Named Reaction Index. Available at: https://www.rsc.org/Merck-Index/reaction/r197/.

[45]  S. A. Glover, A. Rauk, J. Chem. Soc., Perkin Trans. 2 2002, 1740.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XnsVeitLk%3D&md5=5166f843215fa2a75c6b2a994248b795CAS |

[46]  M. Novak, M. J. Kahley, J. Lin, S. A. Kennedy, L. A. Swanegan, J. Am. Chem. Soc. 1994, 116, 11626.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXitlKlt7k%3D&md5=91eb6bd3404197ea02f29eed05b5c3f6CAS |

[47]  M. Novak, J. K. Kayser, M. E. Brooks, J. Org. Chem. 1998, 63, 5489.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXkvFKgsbg%3D&md5=2cef721e5ea6cee0a851b3dd5327574eCAS |

[48]  M. Novak, M. J. Kahley, E. Eiger, J. S. Helmick, H. E. Peters, J. Am. Chem. Soc. 1993, 115, 9453.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3sXmt1Gmsb4%3D&md5=d0f052d4ad72248ba9a5308fc19db87cCAS |

[49]  S. A. Glover, G. Mo, J. Chem. Soc., Perkin Trans. 2 2002, 1728.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XnsVeitL4%3D&md5=4ca98fa1683a735f667178d5c993ab73CAS |

[50]  S. A. Glover, G. P. Hammond, A. M. Bonin, J. Org. Chem. 1998, 63, 9684.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXnsFKls7s%3D&md5=768fea7370a519e67fcdc503bf58264bCAS |

[51]  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=00a46d93482a8128bffb33bde054ad88CAS |

[52]  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=e10cd32d126e0468c60d32ff06719e16CAS |

[53]  R. J. Crawford, R. Raap, J. Org. Chem. 1963, 28, 2419.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF3sXksVOrsr4%3D&md5=ae2f787a5c0bc26584c84f7faebab33bCAS |

[54]  E. Fahr, H. Lind, Angew. Chem. Int. Ed. Engl. 1966, 5, 372.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF28XktFWmurk%3D&md5=6c146af04faf26939317f45c58a0ba59CAS |

[55]  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=44e78acac9db8b3dde42d9d2ff37d442CAS |

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

[57]  K. L Cavanagh, S. A Glover unpublished data.

[58]  S. A. Glover, M. Adams, Aust. J. Chem. 2011, 64, 443.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXkvVCrs7s%3D&md5=c6878282a40fab54e085abdb904fc9e7CAS |

[59]  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=015fa3fad654994f8b47a567b63b1b49CAS |

[60]  S. A. Glover, A. A. Rosser, J. Org. Chem. 2012, 77, 5492.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XnslGqs78%3D&md5=5b5f68ceec5e37d473b54f748ab77105CAS |

[61]  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).

[62]  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=65098d811a19e5e0ee05b00ae65fff53CAS |

[63]  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=b53f6376aa9094d4d847cb7fc5e6cdc2CAS |

[64]  S. A. Glover, A. A. Rosser, A. Taherpour, B. W. Greatrex, Aust. J. Chem. 2014, 67, 507.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXkt1Wrs7g%3D&md5=29705fa9db331cc026843d64950de7f1CAS |

[65]  S. A. Glover, A. A. Rosser, J. Phys. Org. Chem. 2015, 28, 215.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhtVamu73E&md5=b29e7bd3571859ffe1bfc43f76ab7307CAS |

[66]  S. A. Glover, A. A. Rosser, Can. J. Chem. 2016, 94, 1169.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC28XitVSrt7jE&md5=7ad5dd5b99e6e1a8b9c3aeb89f0ba815CAS |

[67]  A. J. Kirby, I. V. Komarov, N. Feeder, J. Chem. Soc., Perkin Trans. 2 2001, 522.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXit1agu7c%3D&md5=b2a79149346badf7cc8ae3fc1e9e284bCAS |

[68]  A. J. Kirby, I. V. Komarov, P. D. Wothers, N. Feeder, Angew. Chem. Int. Ed. 1998, 37, 785.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXis1Ogurw%3D&md5=3085bf35ebd742dfb6f733ba3ca303caCAS |

[69]  I. V. Komarov, S. Yanik, A. Y. Ishchenko, J. E. Davies, J. M. Goodman, A. J. Kirby, J. Am. Chem. Soc. 2015, 137, 926.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXitFOgsLvK&md5=f09fe5cac581cf94a68daf54f46a38b3CAS |

[70]  S. A. Glover, A. A. Rosser, R. M. Spence, Aust. J. Chem. 2014, 67, 1344.
         | 1:CAS:528:DC%2BC2cXhsVyntrbP&md5=d2787b2a1d88fda580c3146eaf9457e2CAS |