Aziridines continue to offer structural fascination, as well as provide important synthetic intermediates in the preparation of biologically active compounds. We are interested in methods for the divergent stereospecific synthesis of aziridine derivatives by functionalization of the intact aziridine ring. This presentation will present our strategy to achieve this via iodoaziridines, which offer facile access to aziridinyl anions and aziridinyl radicals.The first preparation of iodo-aziridines will be discussed. This novel functional group is formed with complete diastereoselectivity from simple imines using diiodomethyllithium. Alkyl and aryl substituted aziridines can be accessed with excellent yields and excellent cis-selectivity. Lithium-iodine exchange affords the corresponding aziridinyl-lithium that can be trapped at low temperature with complete retention of configuration using a wide range of carbon and heteroatom electrophiles. Furthermore, aziridinyl radicals can be generated from the iodoaziridine, which undergo radical substitution. This mode of reactivity provides aziridine products with high trans-selectivity via a planar radical intermediate. The origin of the stereochemical outcomes at each stage will be discussed.

Synthesis and functionalization of iodoaziridines: Divergent synthesis of aziridines by functionalization of the intact ring

248th National Meeting (2014)

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