University of Vermont ScholarWorks @ UVM Graduate College Dissertations and Theses Dissertations and Theses 2017 Generation Of Electron Deficient Carbodiimides And Their Application In The uaG nidine Forming, Zwitterionic 1,3-Diaza-Claisen Rearrangement Joel Walker University of Vermont Follow this and additional works at: https://scholarworks.uvm.edu/graddis Part of the Organic Chemistry Commons Recommended Citation Walker, Joel, "Generation Of Electron Deficient Carbodiimides And Their Application In The uaG nidine Forming, Zwitterionic 1,3-Diaza-Claisen Rearrangement" (2017). Graduate College Dissertations and Theses. 674. https://scholarworks.uvm.edu/graddis/674 This Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks @ UVM. It has been accepted for inclusion in Graduate College Dissertations and Theses by an authorized administrator of ScholarWorks @ UVM. For more information, please contact
[email protected]. GENERATION OF ELECTRON DEFICIENT CARBODIIMIDES AND THEIR APPLICATION IN THE GUANIDINE FORMING, ZWITTERIONIC 1,3-DIAZA- CLAISEN REARRANGEMENT A Dissertation Presented by Joel Walker to The Faculty of the Graduate College of The University of Vermont In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Specializing in Chemistry January, 2017 Defense Date: October 18, 2016 Dissertation Examination Committee: José S. Madalengoitia, Ph.D., Advisor Adrian Del Maestro, Ph.D., Chairperson Adam Whalley, Ph.D. Matthew Liptak, Ph.D. Cynthia J. Forehand, Ph.D., Dean of the Graduate College ABSTRACT The 1,3-diaza Claisen rearrangement was initially discovered by the Madalengoitia group in the early 2000s. Tertiary, allylic, amines nucleophilically add to the carbon of a heterocumulene (isocyanate, isothiocyanate, or carbodiimide) to generate a zwitterion which then undergoes [3,3]-sigmatropic rearrangement.