BICYCLIC METHYLENE AZIRIDINE IN REACTIONS WITH C- AND N-NUCLEOPHILES
DOI:
https://doi.org/10.15421/jchemtech.v31i3.278814Keywords:
azaheterocycles, 1,4-vinylation, vinylmagnesium bromide, aminolysisAbstract
In recent years, various catalytic synthetic methods, starting with allenes, have been developed to produce a wide range of bicyclic methylene aziridines (MA). MA are valuable intermediates for the preparation of complex amine-containing stereotriads, tetrads, and heterocycles potentially useful in the synthesis of natural products and pharmaceuticals. This work reports the possibilities of using ring opening reactions of MA in the synthesis of biologically relevant heterocyclic motifs such as aziridineurea, 2H-azirine and 4,5-disubstituted oxazolidin-2-one. We performed detailed studies on the reaction between model MA with vinylmagnesium bromide and found that along with formal nucleophilic vinylic substitution product minor fraction of 2-methyl-1-(3-methyl-2H-azirin-2-yl)propyl pent-4-enoate was isolated. We showed that investigated reactions are stereoretentive, ruling out a SNVπ pathway, but the detailed mechanism remains open to speculation. Thus, reactivity patterns shown here for MA reactions can be useful in predicting reaction paths with other C- and N-nucleophiles. 2D NMR spectra of the key products were studied in detail including COSY, NOESY and HSQC experiments.
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