Beckmann Rearrangement of 3-carboxybicyclo[3.3.1]nonane and [3.2.1]octane Oximes


  • Marian Gorichko Department of Chemistry, Taras Shevchenko National University of Kyiv
  • Andriy Bulochnikov Department of Chemistry, Taras Shevchenko National University of Kyiv
  • Olga Ryzhenko Department of Chemistry, Taras Shevchenko National University of Kyiv



Beckmann rearrangement, oxime, bicyclo[3.3.1]nonane, bicyclo[3.2.1]octane, lactam


Regiospecific Beckmann rearrangement of substituted 2-hydroximinonorbornanone carboxylic acids has been investigated. Selective formation of new functionalized 10-oxo-9-azabicyclo[3.3.2]decanes and 7-oxo-6-azabicyclo[3.2.2]nonanes in good yield has been demonstrated. Presence of neighboring carboxylic group allows conducting of Beckmann rearrangement of strained bicyclic compounds


Gawley RE. The Beckmann reactions: rearrangements, elimination-additions, fragmentations and rearrangement-cyclizations. Org. Reactions. New York, John Wiley & Sons; 1988; v35. – Chapter 1.

Nace H, Watterson A. Application of the Beckmann Rearrangement to the Preparation of A-Azapregnane Derivatives1. The Journal of Organic Chemistry 1966;31(7):2109-2115.

Ronchin L, Vavasori A, . On the mechanism of the organocatalyzed Beckmann rearrangement of cyclohexanone oxime by trifluoroacetic acid in aprotic solvent. Journal of Molecular Catalysis A: Chemical 2009;313(1-2):22-30.

Nishiyama H, Sakuta K, Osaka N, Itoh K. Silicon-directed beckmann fragmentation. Catalytic cleavage of cyclic β-trimethylsilylketoxime acetates with trimethylsilyl trifluoromethanesulfonate. Tetrahedron Letters 1983;24(37):4021-4024.

Wolff S, Barany F, Agosta W. Novel photochemical rearrangements of citral and related compounds at elevated temperatures. Journal of the American Chemical Society 1980;102(7):2378-2386.

Narula A, Sethi S. Chiral trans hydrindenones : synthesis of optically pure [3aαH(S), 7aβMe(S)trans-1-methyl-7a-methylhydrindan-1,4-diene-6-one. Tetrahedron Letters 1984;25(6):685-688.

Stevens R, Lawrence D. Camphorae: chiral intermediates fob the total synthesis of steroids. Tetrahedron 1985;41(1):93-100.

Tartaggia S, De Lucchi O, Gambaro A, Zangrando R, Fabris F, Scarso A. Chiral M3L2Self-Assembled Capsules through Metal Coordination of Enantiopure Ligating Benzocyclotrimers: NMR Spectroscopic and ESI Mass Spectrometric Investigation. Chemistry - A European Journal 2013;19(18):5701-5714.

Klinot J, Vystrčil A. Beckmannsche umlagerung von triterpen-3-ketoximen. Collection of Czechoslovak Chemical Communications 1962;27(2):377-386.

Brieskorn C, Hemmer E. Umlagerung von Halogennitrosopinan in 6-Halogencampheroxim. Chemische Berichte 1976;109(4):1418-1423.

Hill R, Gary^ McKinnie B, Conley R, Darby P, van Halbeek H, Holt E. Novel products from Beckmann fragmentation of camphor oxime in polyphosphoric acid. Tetrahedron 1988;44(11):3405-3412.

VerHaeghe D, Weber G, Pappalardo P. Beckmann fragmentation versus Beckmann rearrangement in dehydronorcamphor derivatives. Tetrahedron Letters 1989;30(31):4041-4044.

Hunt P, Moody C. Beckmann rearrangements in the bicyclo[2.2.1]heptan-2-one series. Tetrahedron Letters 1989;30(51):7233-7234.

Krow G, Szczepanski S. Unusual regiochemistry in a beckmann-like rearrangement of camphor. α-Camphidone via methylene migration.. Tetrahedron Letters 1980;21(48):4593-4596.

García Martínez A, Teso Vilar E, García Fraile A, de la Moya Cerero S, Lora Maroto B. Intramolecular-activation evidence for the unexpected Beckmann fragmentation of C(1)-substituted-7-bromonorbornane-2-ones. Tetrahedron 2004;60(42):9447-9451.

Nelson R, McEuen J, Lawton R. .alpha.,.alpha.' Annulation of cyclic ketones. Synthesis of bicyclo [3.2.1]octane derivatives. The Journal of Organic Chemistry 1969;34(5):1225-1229.

Marschall H, Vogel F, Weyerstahl P. Synthese von α-Methylen-δ-lactonen. Chemische Berichte 1974;107(9):2852-2859.

Peters J, van der Toorn J, van Bekkum H. 3,7-disubstituted bicyclo [3.3.1] nonanes—II. Tetrahedron 1974;30(5):633-640.

Armarego WLF, Chai C. Purification of Laboratory Chemicals, 5th Edition; Bultesworth-Heinemann: Oxford, 2003.