Since the pioneering efforts of MacMillan, and others in the field of asymmetric organocatalysis, there has been much growth in the design, synthesis, and application of structurally unique catalysts. Among these catalysts, the chiral imidazolidinones first prepared by MacMillan have proven to be successful in the asymmetric Diels-Alder cycloaddition, the vinylogous Michael-Mukaiyama reaction, the Friedel-Crafts, and other reactions. Our research program is currently focused on working with a class of heterocycles known as oxadiazinones. We have previously employed these oxadiazinones as stoichiometric chiral auxiliaries in the asymmetric aldol addition reaction, but now have an interest in steering these compounds in a new direction. These compounds are structurally related to the MacMillan oxadiazinones and may be potentially used as organocatalysts. This presentation will detail the preparation of a series of oxadiazinones derived from (1R,2S)-ephedrine through a process of reductive amination with p-anisaldehyde, N-nitrosation, lithium aluminum hydride reduction, and cyclization with triphosgene. The oxadiazinones were alkylated with a series of alkyl halides to afford N3-alkylatedoxadiazinones that can have the N4-p-methoxybenzyl substituent removed to afford the oxadiazinones that may serve as organocatalysts.

Design and synthesis of oxadiazinones as tools for asymmetric organocatalysis

255th National Meeting (2018)

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