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Synthesis 2011(10): 1515-1525  
DOI: 10.1055/s-0030-1260006
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

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

Agnes Prechter, Markus R. Heinrich*
Department für Chemie und Pharmazie, Pharmazeutische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Schuhstraße 19, 91052 Erlangen, Germany
Fax: +49(9131)8522585 ; e-Mail: Markus.Heinrich@medchem.uni-erlangen.de ;
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Publikationsverlauf

Received 20 December 2010
Publikationsdatum:
15. April 2011 (online)

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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.

Key words

radical reaction - rearrangement - ketones - carboxylic acids - azo compounds

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

39

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

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.

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.

53

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