Nitrogen-containing stereotriads, compounds with three adjacent stereodefined carbons, are commonly found in biologically important molecules. However, the synthesis of these motifs can be challenging, with respect to both the regio- and stereochemistry of the groups installed. Recently, our group has developed a method for the one-pot synthesis of stereotriads from allenes via an intramolecular aziridination protocol. The method delivers a variety of aminated, all-heteroatom stereotriads, with flexible choice of substituents and high selectivity for a single diastereomer. The work presented here describes the further development of this method to allow selective access to any one of the four possible diastereomers of an O/N/O stereotriad (Figure 1). By manipulating key intermediates in the allene aziridination reaction scheme, divergent stereochemical outcomes can be obtained without the need for chiral reagents to bias selectivity. Additionally, the stereochemistry of the allene precursor can be controlled to give either enantiomer of product, thus providing selective access to all eight potential stereoisomers in this scenario. This presentation will outline the development and scope of this method, as well as its ongoing application to natural product synthesis.

Controlled stereodivergence in the synthesis of O/N/O stereotriads via allene aziridination

246th National Meeting (2013)

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