Syntheses of Heterocycles Utilizing Trimethylsilyldiazomethane

利用三甲基甲硅烷基重氮甲烷合成杂环

• 批准号: 07672281
• 负责人: AOYAMA Toyohiko
• 金额: $ 1.41万
• 依托单位: Nagoya City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07672281/
• 关键词: trimethylsilyldiazomethane; lithium trimethylsilyldiazomethane; alkylidene carbene; 2-oxo-3-pyrroline; 3-pyrroline; 2-pyrroline; pyrrole; benzofuran; o-シロキフェニルアセチレン; C-H挿入反応

Synthesis of heterocycles utilizing trimethylsilyldiazomethane (TMSCHN_2) , a useful reagent for generating alkylidene carbenes from carbonyl compounds, was investigated as follows :1. Lithium trimethylsilyldiazomethane (TMSC(Li)N_2), easily prepared from TMSCHN_2 with n-BuLi or LDA,smoothly reacted with N,N-dialkylamides of alpha-keto acids and N,N-disubstituted alpha-amino ketones to give 2-oxo-3-pyrrolines (C-H insertion products) and 3-pyrrolines (C-H insertion products) in good yields via alkylidene carbene intermediates, respectively.2. TMSC (Li) N_2 easily reacted with beta-amino ketones to give 2-pyrrolines (N-H insertion products) in good yields, which easily underwent oxidation by treatment with manganese dioxide (CMD,chemical manganese dioxide) to afford the corresponding pyrroles.3. TMSC (Li) N_2 smoothly reacted with o-siloxybenzaldehydes and o-siloxyacetophenones to give the corresponding o-siloxyphenylacetylenes via alkylidene carbene intermediates, which afforded benzofurans in good yields by treatment with tetrabutylammonium fluoride. Furthermore, 3-benzofuranmethanols could be obtained when the reaction was performed in the presence of electrophiles such as aromatic and heteroaromatic aldehydes.

利用三甲基甲硅烷基重氮甲烷(TMSCHN_2)合成杂环，三甲基甲硅烷基重氮甲烷是一种从羰基化合物生成亚烷基卡宾的有用试剂，研究如下： 1．三甲基硅基重氮甲烷锂（TMSC(Li)N_2），很容易由TMSCHN_2与n-BuLi或LDA制备，与α-酮酸的N,N-二烷基酰胺和N,N-二取代的α-氨基酮顺利反应，得到2-氧代- 3-吡咯啉（C-H 插入产物）和 3-吡咯啉（C-H 插入产物）产率良好分别通过亚烷基卡宾中间体。2． TMSC(Li)N_2很容易与β-氨基酮反应生成2-吡咯啉(N-H插入产物)，收率良好，经二氧化锰(CMD，化学二氧化锰)处理后很容易氧化，得到相应的吡咯。 3． TMSC(Li)N_2与邻硅氧基苯甲醛和邻硅氧基苯乙酮顺利反应，通过亚烷基卡宾中间体生成相应的邻硅氧基苯乙炔，通过四丁基氟化铵处理得到苯并呋喃，收率良好。此外，当反应在芳香醛和杂芳香醛等亲电子试剂存在下进行时，可以获得3-苯并呋喃甲醇。

项目成果

Hideki Ogawa, Toyohiko Aoyama, and Takayuki Shioiri: "Reaction of Lithium Trimethylsilyldiazomethane with N,N-Dialkylamides of alpha-Keto Acids and N,N-Disubstituted alpha-Amino Ketones" Heterocycles. 42. 75-82 (1996)

Hideki Okawa、Toyohiko Aoyama 和 Takayuki Shioiri：“三甲基甲硅烷基重氮甲烷锂与 α-酮酸和 N,N-二取代 α-氨基酮的 N,N-二烷基酰胺的反应”杂环。

Hideki Ogawa: "Reaction of Lithium Trimethylsilyldiazomethane with N, N-Dialkylamides of α-Keto Acids and N, N-Disubstituted α-Amino Ketones" Heterocycles. 42. 75-82 (1996)

Hideki Okawa：“三甲基甲硅烷基重氮甲烷锂与 α-酮酸和 N，N-二取代 α-氨基酮的 N，N-二烷基酰胺的反应”杂环。 42. 75-82 (1996)

Takayuki Shioiri: "Trimethylsilyldiazomethane : A Useful Reagents for Generating Alkylidene Carbenes and Its Application to Organic Synthesis" 有機合成化学協会誌. 54. 918-928 (1996)

Takayuki Shioiri：“三甲基甲硅烷基重氮甲烷：生成亚烷基卡宾的有用试剂及其在有机合成中的应用”有机合成化学学会杂志 54. 918-928 (1996)。

Takayuki Shioiri and Toyohiko Aoyama: Trimethylsilyldiazomethane ; "Encyclopedia of Reagents for Organic Synthesis" Vol.7, L.A.Paquette (ed.). John Wiley & Sons, Chichester, 5248-5251 (1995)

Takayuki Shioiri 和 Toyohiko Aoyama：三甲基甲硅烷基重氮甲烷；

Takayuki Shioiri: "Trimethysilyldiazomethane:A Useful Reagents for Generating Alkylidene Carbenes and Its Application to Organic Synthesis" 有機合成化学協会誌. 54. 918-928 (1996)

Takayuki Shioiri：“三甲基甲硅烷基重氮甲烷：生成亚烷基卡宾的有用试剂及其在有机合成中的应用”有机合成化学学会杂志 54. 918-928 (1996)。