Synthesis, structure, and oxidative properties of N-(2-iodyl-phenyl)-acylamides: Novel hypervalent iodine reagents bearing pseudo six-membered ring scaffold

ORGN 107

Uladzimir Ladziata, Alexey Y. Koposov, Ka Y. Lo, Jeff Willging, Victor N. Nemykin, and Viktor V. Zhdankin, Department of Chemistry, University of Minnesota Duluth, 10 University Drive, Duluth, MN 55812
During the last decade hypervalent iodine reagents have gained considerable interest as selective and efficient synthetic tools for a number of organic transformations. We wish to report the preparation and reactions of a new class of I(V) hypervalent compounds (2), which were isolated as stable, microcrystalline solids. Preparation of N-(2-iodyl-phenyl)-acylamides (2) was carried out by utilizing a standard acylation protocol followed by alkylation and 3,3-dimethyldioxirane oxidation. Products (2) were characterized by NMR, IR and ESI-MS data. The single crystal X-ray analysis revealed a pseudo benziodoxazin structure with the intramolecular I-O distance of 2.62 . Preliminary experiments indicate that reagents (2) can oxidize alcohols in acetonitrile solution under reflux, the reactivity very largely depending on the substrate structure, and substitution pattern on nitrogen atom adjacent to iodyl moiety. These preliminary results suggest that the pseudo benziodoxazin scaffold reported herein can be used as a lead structure for designing novel regio- and stereoselective hypervalent iodine oxidants.