Preparation, structure and chemistry of new hypervalent iodine based reagents

Organoiodine compounds have been used since the mid 1800's notably in Hofmann's alkylation of amines, the Williamson ether synthesis, and the Wurtz coupling reactions. Iodine in organic compounds occurs most often in monovalent state, with an oxidation state of -1, and forms relatively weak bonds with first row elements, including carbon. Because iodine is the largest, most polarizable halogen and least electronegative of the common halogens, it is also able to form stable polycoordinate, multivalent compounds. The present research is aimed at the preparation and study of new hypervalent iodine reagents and their utilization in organic synthesis.; The following classes of the hypervalent iodine compounds will be studied: hypervalent iodine heterocycles, such as benziodazoles; amino acid derived iodobenzene dicarboxylates and pseudo-cyclic pentavalent iodine derivatives. The structure of these compounds will be investigated by various spectroscopic technique, such as NMR, ESI mass spectroscopy and by X-ray crystallography. Also the structural features of pseudo-cyclic hypervalent iodine derivatives and the influence of secondary bonding in these compounds on their properties will be studied by DFT calculations. The chemical properties of iodobenzene dicarboxylates will be investigated in the reactions of the iodocarboxyation of alkenes as a novel route to stereoselective preparation of cis- and trans-diols. The reactivity of the pentavalent iodine compounds toward oxidation of various functional groups such as alcohols and sulfides will be studied.