Study on the Novel Radical Reactions with Hypervalent Iodine Compounds

高价碘化合物的新型自由基反应研究

• 批准号: 06640762
• 负责人: TOGO Hideo
• 金额: $ 1.28万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06640762/
• 关键词: Radical reaction; Carbon-centered radical; Oxygen-centered radical; Nitrogen-centered radical; (Diacyloxyiodo) arene; Radical cyclization; ラジカルアミネーション; 高配位ヨウ素化合物; ラジカルアルコキシレーション; スルフィド; 光照射反応; ラクトン; カルボン酸; 脱炭酸

Radical reactions are one of the most useful methods for organic synthesis. Therefore, the study on the novel radical reactions with trivalent iodine compounds has been carried out. As a result, it was found that (diacyloxyiodo) arenes which has electron-donating group on a aromatic ring accelerated the radical reactivities under the irradiation with tungsten lamp as shown below,1) conversion of carboxylic acids to the corresponding sulfides in the presence of disulfides,2) conversion of aromatic carboxylic acids to the corresponding gamma-or delta-lactones,3) conversion of alcohols bearing a aromatic ring to the corresponding cyclic ethers,4) conversion of amines bearing a aromatic ring to the corresponding cyclic amines,These reactions proceed via the formation of carbon-, oxygen-, and nitrogen-centered radicals to give the products with a simple operation in good yields. In nature, there are many kinds of important cyclic compounds containing oxygen and nitrogen atoms. Therefore, the present method is very useful for the preparation of these natural products. These results were published in three international Journals in 1995, and the other papers are in preparation for the contribution to the Journals.

自由基反应是有机合成中最常用的方法之一。因此，开展了三价碘化合物与新型自由基反应的研究。结果发现，在芳环上具有供电子基团的（二酰氧基碘）芳烃在钨灯照射下加速自由基反应性，如下所示，1）在二硫化物存在下羧酸转化为相应的硫化物，2）芳族羧酸转化为相应的γ-或δ-内酯，（3）将含芳环的醇转化为相应的环醚;（4）将含芳环的胺转化为相应的环胺。这些反应通过形成碳、氧和氮中心自由基来进行，操作简单，产率高。在自然界中，存在着许多重要的含氧、氮原子的环状化合物。因此，本方法对于制备这些天然产物是非常有用的。这些结果于1995年在三个国际期刊上发表，其他论文正在准备向期刊投稿。

项目成果

H.Togo,T.Muraki,and M.Yokoyama,: "Remote Functionalization (1) : Synthesis of g-and d-Lactones from Aromatic Carboxylic Acids" Tetrahedron Letters. 36. 7089-7092 (1995)

H.Togo、T.Muraki 和 M.Yokoyama，：“远程官能化 (1)：从芳香族羧酸合成 g-和 d-内酯”四面体字母。

H.Togo,S.Ishigami,M.Fujii,and M.Yokoyama: "Synthesis of C-Nuclcosides via Radical Conpling Reaction" Journal of The Chemical Society,Perkin 1. 2931-2942 (1994)

H.Togo、S.Ishigami、M.Fujii 和 M.Yokoyama：“Synthesis of C-Nuclcosides via Radical Conpling Reaction” Journal of The Chemical Society，Perkin 1. 2931-2942 (1994)

H.Togo, T.Muraki, and M.Yokoyama,: "Preparation of Adamantyl Sulfides with [Bis (adamantanecarboxy) iodo] arenes and Disulfides" Synthesis,. 155-157 (1995)

H.Togo、T.Muraki 和 M.Yokoyama，：“用[双（金刚烷羧基）碘]芳烃和二硫化物制备金刚烷基硫醚”合成。

Hideo Togo, Ken Hayashi, and Masataka Yokoyama: "Radical Alkylation of Heteroaromatic Bases with Polysilane Compounds" Bulletin of The Chemical Society of Japan. 67. 2522-2527 (1994)

Hideo Togo、Ken Hayashi 和 Masataka Yokoyama：“杂芳族碱基与聚硅烷化合物的自由基烷基化”日本化学会通报。

H.Togo, Rie Taguchi, and Masataka yokoyama: "Reactivities of [Bis (adamantanecarboxy) iodo] arenes in Substitution and Addition reactions" Journal of The Chemical Society, Perkin. 1. 2135-2139 (1995)

H.Togo、Rie Taguchi 和 Masataka yokoyama：“取代和加成反应中[双（金刚烷羧基）碘]芳烃的反应性”化学学会杂志，珀金。