New Syntetic Methods by use of Organic Sulfur and Selenium

有机硫和硒的合成新方法

• 批准号: 61470086
• 负责人: TORU Takeshi
• 金额: $ 4.1万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470086/
• 关键词: (Selenothiopexroxy)benzoate; Acylation; Anti-Markownikoff Addition; Thioester; Selenothiahomoprotoadamantanone; Oxyselenenylation; Selenocyclization; ラジカル反応; S-アシルフェニルセレノスルフィド; アリルチオベンゾアート; ビニルチオベンゾアート; ビニルセレニド; アシル化反応

We have studied of the scope and limitations of Se-phenyl (selenothioperoxy) benzoates 1 (S-acyl Se-phenyl selenosulfides) as useful organic synthetic reagents and found the following intersting results.i) Selenosulfide 1 could be used as a mild acylating agent of an amino group. Maytenin was convenientyl synthesized from spermidin.ii) Radical reactions of olefins with 1 gave addition products. A characteristic reaction feature of these radical reactions was shown in that all the additions occurred regioselectiveyy in anti-@markownikoff manner as for the phenylseleno group.iii) Seleno-substituted thiahomoprotoadamantanone was prepared by the intramolecular radical cyclization. An unexpected transformation to the vinyl selenide was observed by oxidation of the seleno group of the thiahomoprotoadmantanone.iv) The radical reaction of 1 with allyltin compounds gave allyl thiobenzoate, whereas vinyltin compounds gave either an adduct or a vinyl thiobenzoate depending on the substituent on the starting vinyltins.v) A new method of regioselective oxyselenenylation was accomplished by oxymercuration of an olefin and subsequent selenenylation by 1 vai a free-radical process. Furthermore, the above reaction led to a novel selenocyclization reaction by use of an <alpha>,<beta>-unsaturated ester bearing a terminal olefin as a starting substrate.

我们研究了硒-苯（硒硫过氧）苯甲酸酯（S-酰基硒-苯硫醚）作为有机合成试剂的应用范围和局限性，发现了下列有趣的结果：（1）硒硫醚1可用作氨基的温和酰化剂。以亚精胺为原料，经正戊基化合成美登素。这些自由基反应的一个特征反应特征是，所有的加成反应都以反Markownikoff的方式发生。（3）通过分子内自由基环化反应制备了硒基取代的硫杂高原金刚烷酮。通过硫杂高原金刚烷酮的硒基的氧化，观察到了向乙烯基硒化物的意外转化。iv）1与烯丙基锡化合物的自由基反应得到硫代苯甲酸烯丙酯，而乙烯基锡化合物根据起始乙烯基锡上的取代基产生加合物或硫代苯甲酸乙烯酯。通过烯烃的氧汞化和随后的硒化反应实现了一种区域选择性氧硒化的新方法。此外，上述反应导致了一种新的硒环化反应，通过使用<alpha>，<beta>-不饱和酯轴承作为起始底物的末端烯烃。

项目成果

T.Toru;T.Seko;E.Maekawa;Y.Ueno: J.Org.Chem.

T.Toru；T.Seko；E.Maekawa；Y.Ueno：J.Org.Chem。

Toru, Takuya Seko, Eturo Maekawa, and Yoshio Ueno: "Reaction of Olefins with Se-Phenyl (Selenothioperoxy)benzoate: A New Anti-Markownikoff Benzeneselenenylation" J. Chem. Soc. Perkin Trans. 1. (1988)

Toru、Takuy​​a Seko、Eturo Maekawa 和 Yoshio Ueno：“烯烃与（硒代过氧硫代）苯甲酸硒苯酯的反应：一种新的反马可尼科夫苯硒烯化”J. Chem。

T.Toru;T.Kanefusa;E.Maekawa: Tetrahedron Letters. 27. 1583-1586 (1986)

T.Toru；T.Kanefusa；E.Maekawa：四面体字母。

融健: Bull. Chem. Soc. Japan. (1988)

日本化学学会。

Takeshi Toru, Yoshio Yamada, Tetsuhiro Oshima, Shinji Imao, and Eturo Maekawa: "Selective Acylation of Amines by S-Acyl Se-Phenyl Selenosulfides" Nippon Kagakukaishi. 1442-1446 (1987)

Takeshi Toru、Yoshio Yamada、Tetsuhiro Oshima、Shinji Imao 和 Eturo Maekawa：“S-酰基硒-苯基硒硫化物对胺的选择性酰化”Nippon Kagakukaishi。