No description available.

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. The rearrangements conducted with a carbodiimide generate guanidine-containing skeletons. The guanidine functional group is found in many biologically active products, making it a worthwhile chemical target. To this end, strained, tertiary, allylic, amine 2-benzyl-2-azabicyclo[2.2.1]hept-5-ene reacts with in-situ generated carbodiimides in the 1,3-diaza-Claisen rearrangement to afford structurally interesting bicyclic guanidines. Use of more electron deficient carbodiimides makes these rearrangements more facile; however, there are not sufficient methods for the synthesis of highly electron deficient carbodiimides. The synthesis of such carbodiimides was explored through new synthetic methodologies for the dehydration of ureas and desulfurization of isothioureas and the carbodiimides were used in a series of intermolecular rearrangements with the strained, tertiary, allylic, amine. The new methodologies for the synthesis of electron deficient carbodiimides were then applied to a series of intramolecular substrates, further expanding the 1,3-diaza Claisen rearrangement methodologies. To date series of bicyclic, tricyclic, and monocyclic guanidines of varying structures have been synthesized. The synthetic efforts towards these products are herein described.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Zugl.: Hamburg, Univ., Diss., 2006 u.d.T.: Jürs, Stefan: Die Claisen-Umlagerung von Kohlenhydratderivaten als Methode zum Aufbau hoch funktionalisierter Carbocyclen und Saccharidanaloga / Hergestellt on demand

Thesis (Ph. D.)--University of Wisconsin--Madison, 1940. / Typescript. Includes abstract and vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 85-87, 105).

Thesis (Ph. D.)--Johns Hopkins University, 1928. / Biography.

Thesis (Ph.D.) -- McMaster University, 2001. / [Alpha] in title is a Greek letter. Includes bibliographical references. Also available via World Wide Web.

No description available.

This thesis describes investigations directed towards developing a novel synthetic route to the natural products perophoramidine and the communesins, with particular emphasis placed on the formation of the two vicinal all-carbon quaternary centres contained in these molecules. Chapter 1 introduces perophoramidine and the communesin group of natural products and explains how they are related to the calycanthaceous alkaloids. The isolation of perophoramidine and the communesins is outlined and their biosynthesis is discussed. Specific structural features of these natural products are highlighted before established synthetic strategies are reviewed. Chapter 1 concludes by proposing a novel synthetic route for the synthesis of perophoramidine and the communesins that involves a Claisen rearrangement in the indolo[2,3-b]quinoline system as a key step. Chapter 2 describes model studies on the proposed Claisen rearrangement in an attempt to form a quaternary centre in the indolo[2,3-b]quinoline system. These initial studies did not result in the generation of the desired quaternary centre. However, a detailed understanding of the reactions that occur leads to the design of a new model substrate. Chapter 3 describes studies on the revised model system that result in the formation of the desired quaternary centre using a Claisen rearrangement. The differences between the two systems are discussed before an investigation into the scope of the rearrangement is described. Chapter 3 concludes by describing an investigation into a protecting group strategy that would by required with this synthetic route. Chapter 4 describes investigations into the formation of the second vicinal quaternary centre using a model system. The synthetic routes investigated lead to two separate methods for the formation of the desired quaternary centre. Chapter 5 describes investigations into the effect a C-10 substituent has on the Claisen rearrangement. Additionally, an asymmetric version of the Claisen rearrangement is examined. Chapter 5 culminates in the preparation of an intermediate relevant to an asymmetric synthesis of the communesins.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.