New Development of the Chemistry of N-Ylides and S-Ylides

N-叶立德和S-叶立德化学新进展

• 批准号: 04671301
• 负责人: SATO Yoshiro
• 金额: $ 1.34万
• 依托单位: NAGOYA CITY 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: 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-04671301/
• 关键词: ammonium ylide; sulfonium ylide; Sommelet-Hauser rearrangement; stevens rearrangement; [2,3] sigmatropic shift; ring enlargement; desilylation; fluoride ion; Sommelet-Hauser Rearrangement; Stevens Rearrangement; アンモニウムイリド; Sommelet-Hauser転位; S

Fluoride ion induced desilylation of alpha-trimethylsilyl-substituted ammonium (1, Y=NMe) and sulfonium salts (1, Y=S) gave the corresponding ammonium and sulfonium ylides (2) in quantitative yields.Cyclic ammonium ylides (2, Y=NMe) converted to [2,3] sigmatropic rearrangement products (3) and/or Stevens products (4). Telation of their rations with the stereoisomers of 1 was investigated.Selection of the formation path of 3 or 4 was achieved when the reaction of 1 (Y=NMe) was carried out under UV irradiation or in the presence of DBU.sulfonium ylides (2, Y=S) gave selectively Sommelet-Hauser products.

氟离子诱导 α-三甲基甲硅烷基取代铵 (1, Y=NMe) 和锍盐 (1, Y=S) 的脱甲硅烷基化以定量产率得到相应的铵叶立德和锍叶立德 (2)。 环状铵叶立德 (2, Y= NMe) 转化为 [2,3] σ重排产物 (3) 和/或史蒂文斯产物 (4)。研究了它们与1的立体异构体的配比关系。当1(Y=NMe)在紫外线照射下或在DBU存在下进行反应时，实现了3或4的形成路径的选择。锍叶立德(2 ，Y=S）选择性地给出 Sommelet-Hauser 产品。

项目成果

Yoshiro Sato,et al.: "Rearrangement of N,N-Dimethyl(1- or 2-Naphthylmethyl)ammonium N-Methylides" Chem.Pharm.Bull.42(in press). (1994)

Yoshiro Sato 等人：“N,N-二甲基（1-或 2-萘基甲基）铵 N-甲基化物的重排”Chem.Pharm.Bull.42（印刷中）。

Tetsuya Tanaka,Naohiro Shirai,Junji Sugimori,Yoshiro Sato: "Selection of a Sommelet-Hauser or a Stevens Rearrangement Pathway of N,N-Dimethyl(substituted benzyl)ammonium N-Alkylides" Teh Journal of Organic Chemistry. 57. 5034-5036 (1992)

Tetsuya Tanaka、Naohiro Shirai、Junji Sugimori、Yoshiro Sato：“N,N-二甲基（取代的苄基）铵 N-烷基化物的 Sommelet-Hauser 或 Stevens 重排途径的选择”有机化学杂志。

Yoshiro Sato^*, Naohiro Shirai, Yoshio Machida, Emiko Ito, Takayo Yasui, Yukihisa Kurono, and Keiichiro Hatano: "Rearrangements of 1,6,7-Trisubstituted 2-methyl-1,2,3,4-tetrahydroisoquinolinium 2-Methylides" J.Org. Chem. 57. 6711-6716 (1992)

Yoshiro Sato^*、Naohiro Shirai、Yoshio Machida、Emiko Ito、Takayo Yasui、Yukihisa Kurono 和 Keiichiro Hatano：“1,6,7-三取代的 2-甲基-1,2,3,4-四氢异喹啉鎓 2-甲基化物的重排

Yoshiro Sato,et al.: "Rearrangement of N.N-Dimethyl(pyridylmethyl)ammonium,N,N-Dimethyl-1-methyl-(pyrrolylmethyl)ammonium and N,N-Dimethyl(indolylmethyl)ammonium N-Methylides" J.Chem.Soc.,Perkin Tran.1. in press. (1994)

Yoshiro Sato 等：“N.N-二甲基(吡啶甲基)铵、N,N-二甲基-1-甲基-(吡咯甲基)铵和N,N-二甲基(吲哚基甲基)铵N-甲基化物的重排”J.Chem.

Tomoko Kitano, Naohiro shirai, and Yoshiro Sato^*: "Rearrangement of 3-Methyl-2-(4-substituted phenyl)-1,3-exazolinium 3-Methlides" Chem. Pharm. Bull.40. 768-769 (1992)

Tomoko Kitano、Naohiro shirai 和 Yoshiro Sato^*：“3-甲基-2-(4-取代苯基)-1,3-恶唑啉鎓 3-甲基化物的重排” Chem。