Synthesis 2005(20): 3565-3570  
DOI: 10.1055/s-2005-918429
PAPER
© Georg Thieme Verlag Stuttgart · New York

Formation of O-Allyl Oximes by Reaction of Allylzinc Reagents with α-Chloronitroso Compounds

Sorin V. Filip, Norbert Sewald*
Organic and Bioorganic Chemistry, Department of Chemistry, Bielefeld University, PO Box 100131, 33501 Bielefeld, Germany
Fax: +49(521)106 8094; e-Mail: norbert.sewald@uni-bielefeld.de;
Further Information

Publication History

Received 13 May 2005
Publication Date:
25 October 2005 (eFirst)

Abstract

The reaction of α-chloronitrosocyclohexane with allyl­zinc reagents in THF selectively provides O-allylcyclohexanone oximes in very good yields in an ene type reaction followed by zinc halide elimination. N-Allyl hydroxylamines are formed as minor products via N-allyl nitrones when a nonpolar solvent, e.g. toluene, is employed. In both cases complete allylic transposition with respect to the allylic organozinc reagent is observed. Compared to non-metalated allyl compounds, which give N-allyl nitrones upon reaction with α-chloronitroso compounds, the use of zinc as hydrogen equivalent in an ene type reaction displays a drastic change of reactivity.

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