Design and Development of 1,3-diaza-Claisen Rearrangements

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In this project funded by the Chemical Synthesis Program of the Chemistry Division, José Madalengoitia of the University of Vermont will investigate the 1,3-diaza-Claisen rearrangement as novel method for the synthesis of guanidine compounds. The overall reaction involves the addition of a tertiary allylic amine to a carbodiimide to afford a zwitterionic intermediate that in turn undergoes a 1,3-diaza-Claisen rearrangement. The goals for this project are 1) to determine the optimal carbodiimide reactivity and to then explore optimal carbodiimides in ring expanding and intramolecular rearrangements, 2) to develop a rearrangement that proceeds through a cationic intermediate instead of a zwitterionic intermediate, 3) to develop a palladium-catalyzed rearrangement, and 4) to develop rearrangements in which a new stereocenter is formed stereoselectively. The broader impacts involve the training of graduate and undergraduate students in the area of organic synthesis. In addition, high school students in collaboration with Project SEED will be trained the PI's lab during the summer. Guanidine compounds are important as they have been used as catalysts for a number of reactions and guanidine derivatives have been reported to have a range of biological activities including anti-bacterial and anti-HIV activities. This work will expand the ways in which guanidine compounds can be made and will broaden the range of guanidine compounds that can be easily made. Societal benefits should come from the application of this work to the synthesis guanidine catalysts, guanidine natural products and guanidine pharmaceuticals.