Synthesis and reaction of hypervalent λ3-Iodane-crown ether complexes

Abstract

In this review, we show that intermolecular hypervalent I(III)...O interactions play an essential role in the complexation of organo-λ3-iodanes with crown ethers. In addition to the well-known driving force for the complexation of crown ethers, ion-dipole interaction, and hydrogen bonding interaction, our result provides a new class of interaction in supramolecular chemistry of crown ethers. Both solid state structure analysis and solution chemistry indicate that diaryl-, 1-alkenyl(phenyl)-, 1-alkynyl(phenyl)-, and hydroxy(phenyl)-λ3-iodanes form stable complexes with 18-crown-6 through hypervalent I(III)...O interactions. The complexation not only increases the stability of these hypervalent λ3-iodanes but also holds its high reactivity toward nucleophiles. The complex of hydroxy(phenyl)-λ3 -iodanes with 18-crown- 6 serve as versatile oxidizing agents, especially in water. © 2011 The Pharmaceutical Society of Japan.