Compounds with unusual halogen, boron, and silicon groups as entry point to new reactivity patterns

Abstract

The chemistry of hypervalent iodine has grown rapidly in the last two decades, with iodine (III) and iodine(V) compounds becoming common reagents in a wide range of synthetic applications. Hypervalent organoiodine species exhibits attractive reactivity features, like those of transition metals and for this reason these compounds are considered to be environmentally benign. In this project, two applications of iodine(III) chemistry were studied: transylidation of iodonium ylide, and synthesis of iodine triacetate derivatives. Aryliodonium ylides are organoiodine(III) compounds that have been used in a wide range of synthetic applications such as carbene transfer, fluorination/radiofluorination of aromatic substrates, transylidation among others. In this project the main focus is on the transylidation between iodonium ylides and iodoarene under thermal and catalytical conditions, This reaction might provide an efficient approach to the preparation of potentially “delicate” iodonium ylide species. The second part of the project was centered in the chemistry of iodine tricarboxylates, specifically the iodine triacetate. The general pathway to synthesize (diacetoxyiodo)arenes is via oxidation of the iodoarene precursor using oxidizing agents. Instead, iodine tricarboxylates offer transmetallation as an alternative pathway avoiding the oxidation of sensitive iodoarene precursors, broadening the scope of (diacetoxyiodo)arenes. Nevertheless, iodine tricarboxylates are unstable in the atmosphere and they are light sensitive causing these compounds hard to be handled. Therefore, in this part, derivatives of iodine triacetate were prepared in order to stabilize this compound and at the same time, perform similar reactivity