Can aziridines undergo base-promoted isomerization to allylic amines?

ORGN 75

Monique Pichon, mapichon@xula.edu, Kathleen M. Morgan, kmmorgan@xula.edu, Garry Brown Jr., gbrown@xula.edu, Karen Montgomery, kamontgo@xula.edu, and Kimberly Peterson. Department of Chemistry, Xavier University of Louisiana, 1 Drexel Drive, New Orleans, LA 70125
Allylic amines could, in theory, be obtained by the rearrangement of aziridines in the same fashion as the well-known isomerization of epoxides to allylic alcohols. Past studies have shown that this aziridine rearrangement in THF is not generally productive. The goal of this study is to determine whether reaction conditions can be found in which the formation of allylic amines is favorable.

Our computational results (MP2/6-31+G**//MP2/6-31+G*) show that the gas-phase rearrangement of methyl aziridine to allyl amine is more favorable than rearrangement of propene oxide to allyl alcohol. It was anticipated that using polar aprotic solvent would have important consequences for this reaction, as it does in epoxide rearrangement. However, rearrangement of N-tosyl aziridines in HMPA has been unsuccessful. We are currently exploring whether other substituents on nitrogen will allow the rearrangement to proceed.

 

Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007