Novel Cycloaddition Reactions of Nonvertical Radical Cations

非垂直自由基阳离子的新型环加成反应

• 批准号: 04640506
• 负责人: KAWAMURA Yasuhiko
• 金额: $ 1.41万
• 依托单位: The University of Tokushima
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640506/
• 关键词: Nonvertical radical cation; Nitrone; Oxaziridine; Phosphorus ylide; Sulfur ylide; Hydroxyacetophenone; Photosensitized electron transfer; Single electron transfer; オキサジソジン; ホスホラン; ラジカルカチオン; 転位反応

In order to gain insight into the structure and reactivity of the above novel radical cations, nitrones (1)-oxaziridines (2), stable phosphorus (3) and sulfur ylides (4), and hydroxyacetophenones (5) were chosen as the substrates and photo and thermal single electron-transfer (SET) reactions were studied. The results are summarized as follows :1. Compound 1 and 2 were interconvertable each other depending on the substituent on the aryl group under photosensitized electron-transfer (PET) conditions.2. Ring-opening of 2 were proceeded in a stereoselective manner under PET conditions. It is also applicable to the convenient preparation of sterically hindered 1.3. Although stable 3 are employed for the synthesis in a very limited scope, SET nature of such ylides are focused to enhance the reactivity. The reaction of fluorene substituted 3 with prenyloxybenzene diazonium salt gave dihydrobenzofuran derivative. The reaction proceeded via the SET-radical couplingionic termination sequence. Additionally, (cyclo)addition reactions of 3 with electron-deficient alkenes and alkynes were studied to aim at enhancing the reactivity by charge-transfer nature. Unusual temperature-dependence of NMR of fluorenylideneethylidene substituted 3 was also studied in comparison with the analogously substituted 4.4. Photoreactivity of 5 which usually is unreactive upon photoirradiation were enhanced in the presence of aluminum halides. In one case, bromination of the neighboring alkyl group occurred in anti-Markownikoff manner. In another, remarkable structural conversion into oxabicycloheptenone occurred under PET conditions. The reaction seemed to be proceeded by the SET and the following addition of oxygen.

为了深入了解上述新型自由基阳离子的结构和反应性，硝酸盐（1） - 氧化胺（2），稳定的磷（3）和硫乙酯（4）和羟基乙烯酮（5）被选为底物，光和热单电子传输（套件）。结果总结如下：1。根据光敏的电子转移（PET）条件，化合物1和2互相互相互相互相互相。2。在宠物条件下以立体选择的方式进行2次开环。它也适用于方便的空间阻碍1.3。尽管在非常有限的范围中使用稳定的3用于合成，但这种Ylides的固定性质却集中在增强反应性。氟代替3用前氧苯丁烯盐取代的反应给出了二氢苯并苯呋喃衍生物。反应通过固定的激进耦合离子终止序列进行。另外，研究了3与电子缺陷烷烃和炔烃的（环）添加反应，目的是通过电荷转移性质来增强反应性。还研究了与类似取代的4.4相比，还研究了氟二烯乙基取代3的NMR的异常温度依赖性。在存在铝卤化物的情况下，通常在光辐射时没有反应的5的光反应性增强。在一种情况下，相邻烷基的溴化以抗宣传方式发生。在另一个显着的结构转化为黄杨甲基酮的情况下发生在宠物条件下。该反应似乎是通过集合和以下氧气进行的。

项目成果

Y.Kawamura: "Deoxygenation of Some Arylnitrones Induced by Phtosensitized Electron Transfer" Chem. Lett.(in press). (1994)

Y.Kawamura：“光敏化电子转移诱导的一些芳基硝酮的脱氧”化学。

Y.Iwano: "Stereoselective Ring Opening of Geometrically constrained 3,3-Diary-1-2-t-butyloxaziridines by Photosensitized Electron Transfer" (in preparation). (1994)

Y.Iwano：“通过光敏电子转移对几何约束的 3,3-Diary-1-2-t-丁基氧氮丙啶进行立体选择性开环”（准备中）。

Y.Iwano: "Photosensitized Electron-transfer Reaction of 3-Aryl-2-methyloxaziridine:Direct Deoxygenation from the Isomeric Arylnitrone" Bull.Chem.Soc.Jpn.67(submitted). (1994)

Y.Iwano：“3-芳基-2-甲基氧氮丙啶的光敏电子转移反应：异构体芳基硝酮的直接脱氧”Bull.Chem.Soc.Jpn.67（已提交）。

Y.Kawamura: "Photosensitized Oxygenation of Diarylmethylenetriphenylphosphoranes" Phosphorus, Sulfur, and Silicon. 73. 121-125 (1992)

Y.Kawamura：“二芳基亚甲基三苯基膦的光敏氧化”磷、硫和硅。

Y.Iwano: "Stereoselective Ring Opening of Geometrically Constrained 3,3-Diaryl-2-t-butyloxaziridines by Photosensitized Electron Transfer" J.Org.Chem.59(発表予定). (1994)

Y.Iwano：“通过光敏电子转移实现几何约束的 3,3-二芳基-2-t-丁基氧氮丙啶的立体选择性开环”J.Org.Chem.59（待提交）。