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Umpolung heteroatom transformations mediated by Iodine(iii) reagents: novel reagent development and synthetic applications
Sedler , Cassandra
Sedler , Cassandra
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2025-12
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Chemistry
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The concept of umpolung or reverse polarity is a pivotal component in accessing new, otherwise impossible, bond disconnection and expanding chemical space. The development of umpolung strategies for the construction of valuable C-heteroatom bonds is of utmost importance to synthetic chemists. In this area, hypervalent Iodine(III) reagents acquire an esteemed role due to their unique umpolung reactivity, ease of handling and environmentally benign conditions. This dissertation focuses on the development of I(III) mediated heteroatom transformations and outlines the design and synthesis of new N-ligated cyclic, non-symmetrical I(III) compounds for efforts in investigating their potential as umpolung aminating reagents.
Chapter 1 of this dissertation serves as an introduction and background to hypervalent Iodine(III) reagents including the Nitrogen-ligated (Bis)cationic I(III) reagents (N-HVIs).
In Chapter 2, a novel strategy for the synthesis of phenol derivatives via oxidative rearrangement of acyclic secondary alcohols has been developed. By leveraging an umpolung activation platform developed in our laboratory with I(III) reagents, excellent selectivity for C–O bond migration over competitive oxidation was achieved. The resulting acetals can be readily converted to phenols via a one-pot hydrolysis, giving access to challenging phenol derivatives from simple substrates.
Chapter 3 discusses the design of non-symmetrical I(III) (N,X-HVI) reagents bearing one N-heterocyclic and one anionic X- ligand and highlights efforts in the investigation of N,X-HVIs single electron reduction potential for the generation of (Hetero)arene N-centered radical cations (HA-NRCs) is outlined. Initial investigation into the fundamental reactivity of the synthesized N,X-HVI reagents has been demonstrated in the amination of benzene as a model transformation. Efforts towards establishing a baseline reactivity profile of synthesized N,X-HVIs were examined in I(III) mediated transformations including olefin and alcohol activations as well as C-H aminations. This chapter outlines foundational discoveries into the unexplored synthetic applications of N,X-HVI reagents in organic synthesis.
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