Oxidation Iodobenzene With Tetra-n-butyl Ammonium Iodide [1,3] Synthesis Of Cyclopropane And Aziridines Oxidative Cyclization Reaction Initiator

This thesis focused on the cyclization reaction induced by the combination of PhIO and TBAI. We developed synthesis methods based on the [1,3] oxidative cyclization which induced under the PhlO/TBAI condition, and synthesized compounds of cyclopropanes and aziridines.In the first part, we developed a facile synthesis of cyclopropanecarboxylates through a tandem PhlO/TBAI induced oxidative cyclization and a subsequent neighboring group-assisted decarboxylation of the Michael adducts of 2-cyanoacetamides withα,β-unsaturated malonates. Furthermore, it affords the desired highly functionalized cyclopropanes in moderate to good yields and with excellent diastereoselectivities. The products were proved to be cis-configuration with the X-ray Diffraction analysis. According to the transformation among three compounds which we got from the same material, we raised a plausible reaction mechanism that the reaction underwent an intramolecular oxidative cyclization and a subsequent amide-assisted decarboxylation. In addition, the reaction proceeds smoothly under mild conditions and with good functional group tolerance.In the second part, we studied an efficient [1,3] oxidative cyclization of amidoalkylation adducts of activated methylene compounds with the combination of PhIO and a catalytic amount of TBAI under neutral conditions. And we found that the main products would be oxazolines when we changed part of the constitution of the beginning compounds from diethyl malonate to acetylacetone. The reaction also affords products in moderate to excellent yields. The scope and synthetic application are continued to be studied.