Development and Synthetic Applications of [1,3] and [3,3] Rearrangements of O-Vinyl Oximes

University Of Illinois At Chicago, Chicago IL

Investigators

Abstract

In this project, funded by the Chemical Synthesis Program of the Chemistry Division, Professor Laura L. Anderson of the Department of Chemistry at the University of Illinois at Chicago will explore the synthetic applications of the [1,3] and [3,3] rearrangements of O-vinyl oximes for more efficient access to important stereodefined organic fragments such as alpha-amino ketones, 1,4-imino ketones, beta-amino alcohols, gamma-amino alcohols, and heterocycles. Prior use of O-vinyl oximes in organic synthesis has been hampered by a lack of general methods for their preparation. This program builds on recent discoveries of simple methods for the preparation of O-vinyl oximes and initial observations of the tunability of their rearrangement reactions. Collection of fundamental reactivity and mechanistic data will be used to guide the development of stereoselective and catalytic processes and to harness the potential of these underutilized important synthons. Rearrangement products of O-vinyl oximes will be further derivitized using the stereochemical information set during the sigmatropic rearrangements to provide rapid access to complicated, stereodefined, organic fragments. This project could transform an unused organic compound into a valuable and versatile organic synthon, providing new tools for the retrosynthetic analysis of synthetic targets and the elucidation of new efficient pathways to important pharmaceuticals and materials. The fundamental studies outlined in the proposal could rapidly elucidate the most potent applications of these underutilized intermediates and this approach to synthetic method development will also function as a means to train an ethnic and gender diverse group of graduate and undergraduate students to find creative solutions to synthetic challenges and prepare them to positively impact the chemical community.