Development of Generation Method of Unstable Chemical Species Using Characteristics of Heteroatom Compounds

利用杂原子化合物的特性开发不稳定化学物质的生成方法

• 批准号: 10450347
• 负责人: SONODA Noboru
• 金额: $ 8.96万
• 依托单位: kansai University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10450347/
• 关键词: Selenium; Vinyl radical; Nitro compound; Nitrene; ヘテロ原子; 一酸化炭素; 1,2,3-セレナジアソール

We have investigated the new generation method of unstable chemical species by the use of the characteristics of heteroatom compounds and the utilization of these species in organic synthesis. In the course of our study, we found that nitre or nitrenoid species were generated efficiently by the reduction of aromatic nitro compounds with carbon monoxide in the presence of a catalytic amount of selenium. N-Heterocyclic compounds such as indols and 4(3H)-quinazolinones were synthesized by the selenium-catalyzed reaction of 0-nitrostyrenes and 0-nitrobenzoylamides with carbon monoxide in moderate to good yields. In addition, we have also developed the new generation method of vinyl radical via the thermal decomposition of 1,2,3-selenadiazoles. When 1,2,3-selenadiazoles were treated with olefins under thermal condition, the addition of vinyl radical generated in situ to carbon-carbon double bond and followed by intramoleculer cyclization proceeded efficiently to give the corresponding dihydroselenophenes in moderated to good yields. This reaction was hardly promoted by the addition of a catalytic amount of organostannyl radical.

本文利用杂原子化合物的特性，研究了不稳定物种的新生成方法，以及这些物种在有机合成中的应用。在我们的研究过程中，我们发现，硝基或nitrenoid物种有效地产生的芳香族硝基化合物与一氧化碳在催化量的硒的存在下还原。以硒为催化剂，邻硝基苯乙烯和邻硝基苯甲酰胺与CO反应，合成了吲哚和4（3 H）-喹唑啉酮等N-杂环化合物。此外，我们还开发了通过1，2，3-硒二唑热分解产生乙烯基自由基的新方法。当1，2，3-硒二唑与烯烃在热条件下反应时，原位生成的乙烯基自由基与碳-碳双键的加成反应和随后的分子内环化反应有效地进行，从而以较好的产率得到相应的二氢硒吩。加入催化量的有机锡基自由基几乎不促进该反应。

项目成果

Yutaka Nishiyama: "Selective Synthesis of 1-Alkoxy-3-phenylseleno-1-alkenes and 3-phenylselenoalkanals by the Reaction of Diisobutylaluminum Phenylselenelate with α,β-Unsatunited Acetals" Tetrahedron Letters. 39. 8685-8686 (1998)

Yutaka Nishiyama：“通过苯基硒酸二异丁基铝与 α,β-不饱和缩醛的反应选择性合成 1-烷氧基-3-苯基硒基-1-烯烃和 3-苯基硒烷醛”，Tetrahedron Letters 39。8685-8686 (1998)。

Noboru Sonoda et al.: "Synthesis of Indoles : Selenium-Catalyzed Reductive N-Heterocyclization of 2-Nitrostyrenes with Carbon Monoxide"Tetrahedron Letters. 40. 5717-5720 (1999)

Noboru Sonoda等人：“吲哚的合成：硒催化的2-硝基苯乙烯与一氧化碳的还原N-杂环化”四面体快报。

Y. Nishiym,a Y. Kishimoto, K. Itoh and N. Sonoda: "Regioselective Alkylation of 1-Alkoxy-3-phenylseleno-1-alkanes"Synlett. 5. 611-613 (1999)

Y. Nishiym、Y. Kishimoto、K. Itoh 和 N. Sonoda：“1-烷氧基-3-苯基硒代-1-烷烃的区域选择性烷基化”Synlett。

Noboru Sonoda et al.: "Catalytic Use of Organostannyl Radical:The Reaction of 1,2,3-Selenadiazole with Olefins in the Presence of a Catalytic Amount of Tributyltin Hydride"Tetrahedron Letters. 40. 6293-6296 (1999)

Noboru Sonoda 等人：“有机锡烷基自由基的催化用途：在催化量的三丁基氢化锡存在下，1,2,3-硒二唑与烯烃的反应”四面体字母。

Noboru Sonoda: "Regioselective Alkylation of 1-Alkoxy-3-Phenylseleno-1-alkenes" SYNLETT. (印刷中).

Noboru Sonoda：“1-烷氧基-3-苯基硒代-1-烯烃的区域选择性烷基化”SYNLETT（正在出版）。