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

新型手性有机高价碘化合物的制备及其手性氧化应用的研究

基本信息

批准号：
10640511
负责人：
TOGO Hideo
金额：
$ 2.05万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

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.

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：在碘原子上带有手性烷氧基配体，B型：碘原子上的轴向手性，以及它们在底物手性氧化中的合成用途。在第一年，合成了邻位带有烷氧基手性中心的新型碘代芳烃，并将其转化为相应的环状三价碘形式（A型），研究了其氧化硫醚的反应活性。在第二年，进行了在碘原子上具有轴向手性中心的有机三价碘化合物（B型）的制备。所有这些新化合物均经~ 1H-NMR、~ <13>1C-NMR和X-射线晶体分析表征。近年来，通过手性碘代芳烃的氧化反应制备了带有烷氧基配体的手性三价碘化合物（A型），并通过硫醚的手性氧化反应以较好的收率得到了相应的亚砜。e.实际上，目前的研究结果对于手性三价碘化合物手性氧化的实际应用是不够的。这对于设计优良的手性有机高价碘化合物进行氧化反应具有一定的指导意义。