Synthesis of azaheterocycles from oxime derivatives
Department of Chemistry, Graduate School of Science,
The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Abstract: Electrophilic amination of Grignard reagents has been
accomplished by using O-sulfonyloximes as amination reagents.
Benzophenone O-sulfonyloxime derivatives react with Grignard
reagents on sp2 nitrogen, yielding primary amines by successive
hydrolysis of the resulting N-alkylimines.
Various cyclic imines are synthesized by Pd-catalyzed reaction from
olefinic oxime derivatives. That is, treatment of O-pentafluorobenzoyloximes
of olefinic ketones with a catalytic amount of Pd(PPh3)4
and triethylamine affords nitrogen-containing heterocycles, such as
pyrroles, pyridines, isoquinolines, spiro-imines, and aza-azulenes.
This reaction proceeds via the initial formation of alkylideneaminopalladium(II)
species generated by oxidative addition of the oximes to the Pd(0) complex,
and the following intramolecular amination on the olefinic moiety.
Cyclic imines are prepared from g,d-unsaturated
O-acetyloximes by treatment with acetic acid and 1,4-cyclohexadiene
in the presence of a catalytic amount of 1,5-naphthalene-diol. g,d-Unsaturated
ketone O-methoxycarbonyloximes are transformed to 2-bromomethyl-3,4
dihydro-2H-pyrroles by the action of a catalytic amount of Cu(I)
bromide dimethyl sulfide complex and lithium bromide.
*Lecture presented at the 14th International Conference
on Organic Synthesis (ICOS-14), Christchurch, New Zealand, 14-18 July
2002. Other presentations are published in this issue,
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