Investigation of Reactivities of Electron Deficient Olefins and its Application to Organic Synthesis

缺电子烯烃的反应活性研究及其在有机合成中的应用

• 批准号: 60430008
• 负责人: SERA Akira
• 金额: $ 16万
• 依托单位: Kobe University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-60430008/
• 关键词: Titanium trichloride reduction; Electroreduction; Nitroolefin; Dicyanoolefin; Nitrile; High pressure cycloaddition; チオアセタール化触媒; ニトロオレフィン; シアノオレフィン; 電解還元; 置換インデン合成; アザブタジエン; 三塩化チタン; ピロール; ジビニルアミン; イソオキサゾール; ピラゾール; ヘテロ環合成

1. Titanium Trichloride Mediated Reduction of Nitro-, and Dicyanoolefins:Aqueous titanium trichloride was found to reduce nitorolefins to pyrroles and/or divinyl amines in moderate yields. Dicyanoolefins were also reduced to give five menbered cyclic eneaminonitriles.2. Electroreduction of Nitroolefins in the Presence of Titanium Tetrachloride:Electroreduction of nitroolefins was achieved in the presence of titanium tetrachloride in DMF to yield corresponding nitriles in high yields. Nitroolefins can be easily prepared by means of condensation of aldehydes with nitromethan, and hence the present reduction offers a new synthetic method of one carbon elongated nitriles from easily available aldehydes.3. High Pressure cycloaddition of FuranThe Diels-Alder reaction of furan with dialkyl acetxymethylenemalonate did not proceed at conventional conditions. However, the reaction took place under high pressure of 1 GPa to give an adduct. 7-oxabicyclo[2.2.1]heptene derivative, from which a precursor of C-ribonucleoside was synthesized stereospecifically in a high yield.

1.三氯化钛介导的硝基-和二氰基烯烃的还原：发现含水三氯化钛以中等产率将硝基烯烃还原为吡咯和/或二乙烯基胺。二氰基烯烃也被还原得到五元环烯胺腈.在四氯化钛存在下硝基烯烃的电还原：在DMF中，在四氯化钛存在下实现硝基烯烃的电还原，以高产率产生相应的腈。醛与硝基甲烷缩合可以方便地制备硝基烯烃，因此本还原反应提供了一种由易得的烷烃合成一碳长腈的新方法.呋喃的高压环加成呋喃与乙酰氧基亚甲基丙二酸二烷基酯的Diels-Alder反应在常规条件下不进行。然而，反应在1GPa的高压下进行，得到加合物。7-氧杂双环[2.2.1]庚烯衍生物，由其以高产率立体特异性地合成C-核糖核苷的前体。

项目成果

A. Sera: "High Pressure Asymmetric Michael Addition of Thiols, Nitromethane, and Methyl oxoindancarboxylate to Enones." J. Org. Chem.53. (1988)

A. Sera：“硫醇、硝基甲烷和氧代茚满甲酸甲酯与烯酮的高压不对称迈克尔加成”。

Y. Kamitori: "Selective Protection of Carbonyl Compounds. Silica Gel Treated with Thionyl Chloride as an Effective Catalyst for Thioacetalization." J. Org. Chem.51. 1427-1431 (1986)

Y. Kamitori：“羰基化合物的选择性保护。用亚硫酰氯处理的硅胶作为硫缩醛化的有效催化剂。”

M. Hojo: "A Useful One-step Synthesis of beta-Thioacetylvinyl Ethers and Trihaloacetylketene Acetals." Synthesis. 1013-1014 (1986)

M. Hojo：“一种有用的一步合成 β-硫代乙酰乙烯基醚和三卤乙酰乙烯酮缩醛。”

R. Goto: Chemistry of Monosaccharides. Maruzen Publisher, 280 (1988)

R. Goto：单糖化学。

M.Hojo: Tetrahedron Letters. 27. 353-356 (1986)

M.Hojo：四面体字母。