Study on the Preparation of Novel and Chiral Organohypervalent Iodine Compounds and Their Use for Chiral Oxidation

基于有机高价碘化合物对官能团转化的高反应性，本研究的目标是制备新型手性三价碘化合物；A型：碘原子上有手性烷氧基配体，B型：碘原子上有轴向手性，它们的合成用途是手性氧化底物。第一年，制备了手性中心为o位烷氧基的新型碘芳烃，并将其转化为相应的环三价碘（a型），研究了其对硫化物的氧化反应性。第二年，制备了碘原子（B型）轴向手性中心的有机三价碘化合物。所有这些新化合物都通过^1H-NMR， ^<13>C-NMR进行了表征，最后对化合物进行了x射线晶体分析。去年，通过手性碘芳烃的氧化，建立了含烷氧配体（A型）的手性三价碘化合物的制备方法，并对硫化物进行了手性氧化，得到了相应的亚砜，产率高，e值适中。实际上，目前的结果不足以用现有的手性有机三价碘化合物进行手性氧化的实际应用。然而，这些结果对于设计良好的手性有机高价碘氧化化合物是有用的。

Based on the high reactivity of organo-hypervalent iodine compounds for functional group conversion, the target of the present study is that the preparation of novel chiral trivalent iodine compounds ; type A : bearing a chiral alkoxy ligand on the iodine atom, type B : axial chirality on the iodine atom, and their synthetic use for the chiral oxidation of substrates.At the first year, the preparation of novel iodoarenes bearing a chiral center of alkoxy group at the ο-position, and the conversion to the corresponding cyclic trivalent iodine form (type A) were carried out, and the reactivity for the oxidation of sulfides were studied. At the second year, the preparation of organo-trivalent iodine compounds bearing an axial chiral center at the iodine atom (type B) were carried out. All these new compounds were characterized by ^1H-NMR, ^<13>C-NMR, and finally X-ray crystal analysis of the compounds. At the last year, the preparation of chiral trivalent iodine compounds bearing an alkoxy ligand (type A) was established via the oxidation of the chiral iodoarenes, and the chiral oxidation of sulfides was carried out to give the corresponding sulfoxides in good yields with moderate e. e. Actually, the present results are not enough for the practical use of chiral oxidation with the present chiral organo-trivalent iodine compounds. However, it is useful results for the design of good chiral organo-hypervalent iodine compounds for oxidation.