Active Fluoro-intermediate for Fluorinated Heterocycles

含氟杂环活性含氟中间体

• 批准号: 04453101
• 负责人: UNEYAMA Kenji
• 金额: $ 4.29万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 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-04453101/
• 关键词: Fluoro-compound; Fluorination; Electrolysis; フッ素化合物; フッ素化; イミドイルハライド; トリフルオロメチル化; トリフルオロ酢酸

Trifluoroacetimidoyl metals (Li, Zn, Pd) and telluride have been prepared as precursors for the trifluoroacetimidoyl carbanion and the corresponding radicals and have been employed for the synthesis of fluorinated nitrogen heterocycles. Photolysis of the telluride leads to homolytic cleavage of the C-Te bond to generate the desired trifluoroacetimidoyl radical which undergoes intramolecular cyclization. The reaction provided 3-oxy-2-trifluoro methyl indols (3). Meanwhile, palladium catalyzed carboalkoxylation of the trifluoroacetimidoyl iodides and subsequent alkylation and hydrogenation provided various kinds of fluorinated -aminoacids. Lithium-iodine exhange reaction of the iodides generated the acetimidoyl lithium which is stable below -65 C and alkylated. By these newly developed methods, some interesting heterocycles (2) - (4) have been synthesized.

制备了三氟乙酰亚氨基金属(Li，Zn，Pd)和碲化物作为三氟乙酰亚氨基碳负离子和相应自由基的前驱体，并用于合成含氟氮杂环化合物。碲化物的光解导致C-Te键的均裂断裂，生成所需的三氟乙酰亚氨基，该自由基经历分子内环化。反应生成3-氧基-2-三氟甲基吲哚(3)。同时，钯催化的三氟乙酰亚胺基碘的碳烷氧基化以及随后的烷基化和氢化提供了各种含氟氨基酸。碘与锂的交换反应生成了在-65℃以下稳定的烷基化的乙酰亚胺基锂。用这些新开发的方法合成了一些有趣的杂环(2)-(4)。

项目成果

Kenji Uneyama: "Trifluoroacetimidoyl Lithium" Tetrahedron Letters. 34. 1941-1944 (1993)

Kenji Uneyama：“三氟乙酰亚氨基锂”四面体字母。

Kenji Uneyama: "Generation and Reaction of (N-Aryltrifluoroacetimidoyl)zinc Halide" Bull.Chem.So.Jpn. 67. 300-303 (1994)

Kenji Uneyama：“(N-芳基三氟乙酰亚氨基)卤化锌的生成和反应”Bull.Chem.So.Jpn.

K.Tamura,H.Mizukami,K.Maeda,H.Watanabe K.Uneyama: "One-Pot Synthesis of Trifluoroacetimidoyl Halides" Journal of Organic Chemistry. 58. 32-35 (1993)

K.Tamura，H.Mizukami，K.Maeda，H.Watanabe K.Uneyama：“三氟乙酰亚氨基卤化物的一锅合成”有机化学杂志。

宇根山健治: "モノおよびジフルオロ化反応最近の進展" 有機合成化学協会誌. 51. 232-246 (1993)

Kenji Uneyama：“单氟化和二氟化反应的最新进展”合成有机化学学会杂志 51. 232-246 (1993)。

K.Uneyama,K.Sugimoto: "N-Substituted 2,2,2,-Trifluoroethanimidic Acid 1-Methyl-ethylidene Hydrazides as Synthetic Blocks for Trifluoro-methylated Nitrogen Heterscydes:" Journal of Organic Chemistry. 57. 6014-6019 (1992)

K.Uneyama、K.Sugimoto：“N-取代的 2,2,2,-三氟乙亚胺酸 1-甲基亚乙基酰肼作为三氟甲基化氮杂环的合成嵌段：”有机化学杂志。