Development of New Methods for Carbonylation by Free-Radical Reactions

自由基反应羰基化新方法的开发

• 批准号: 04453087
• 负责人: SONODA Noboru
• 金额: $ 4.61万
• 依托单位: Osaka 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-04453087/
• 关键词: free-radical; carbonylation; carbon monoxide; tin radical; silyl radical; formylation; cyclization; acyl radical; ラジカルカルボニル化; 有機ハロゲン化物; アルデヒド; 非対称ケトン; ミクロペンタノン; スズヒドリド; シクロペンタノン

A novel carbonylation method based on free-radical reactions has been developed. Acylradicals, generated by the addition of alkyl free-radicals to carbon monoxide, have been effectively trapped by tin hydride. Through this sequence, the free-radical formylation of organo halides to the corresponding aldehydes was realized. When an alkene was also present in the reaction system, the trapping of the alkyl free-radical by carbon monoxide to form an acyl free-radical and the subsequent addition of that radical to the alkene took place efficiently to give and unsymmetrical ketone. Tris(trimethylsily)silane can also be used for a free-radical mediator. This sequence represents a unique method for the double alkylation of carbon monoxide. Carbonylative cyclizations to give cyclopentanones can also be affected starting with 4-pentenyl halides. All of these findings that free-radical carbonylation is useful method for the introduction of carbon monoxide into organic molecules.

提出了一种基于自由基反应的羰基化新方法。氢化锡能有效地捕获由烷基自由基与一氧化碳加成产生的酰基自由基。通过这一过程，实现了卤代有机化合物对相应醛的自由基加成反应。当烯烃也存在于反应体系中时，一氧化碳捕获烷基自由基以形成酰基自由基，并且随后将该自由基加成到烯烃上，有效地发生以得到不对称酮。三（三甲基甲硅烷基）硅烷也可用于自由基介体。该序列代表了一氧化碳双烷基化的独特方法。也可以从4-戊烯基卤化物开始进行羰基化环化以得到环戊酮。这些发现表明自由基羰基化是将一氧化碳引入有机分子的有效方法。

项目成果

Kiyoshi Ikura, Ilhyong Ryu, Nobuaki Kambe, Noboru Sonoda: "Room Temperature Isomerization of Silioxycyclopropanes to Silyl Ethers of 2-Methylenealkanols Catalyzed by Zeisse's Dimer" J.Am.Chem.Soc.114. 1520 (1992)

Kiyoshi Ikura、Ilhyong Ryu、Nobuaki Kambe、Noboru Sonoda：“蔡司二聚体催化的硅氧基环丙烷室温异构化为 2-亚甲基烷醇的甲硅烷基醚”J.Am.Chem.Soc.114。

Kiyoshi Ikura: "Room Temperature Isomerization of Siloxycyclopropanes to Silyl Ethers of 2-Methylenealkanols Catalyzed by Zeise's Dimer" Journal of the American Chemical Society. 114. 1520-1521 (1992)

Kiyoshi Ikura：“Zeise 二聚体催化的甲硅烷氧基环丙烷室温异构化为 2-亚甲基烷醇的甲硅烷基醚”美国化学会杂志。

Li-Biao Han, Nobuaki Kambe, Akiya Ogawa, Ilhyong Ryu, Noboru Sonoda: "Reaction of Tetraorganyltelluriums with Acetylenes" Organometallics. 14. 474 (1993)

Li-Biao Han、Nobuaki Kambe、Akiya Okawa、Ilhyong Ryu、Noboru Sonoda：“四有机碲与乙炔的反应”有机金属。

Ilhyong Ryu: "Free-Radical Carbonylation by TTMSS Mediated Process" Synlett. 143-145 (1993)

Ilhyong Ryu：“TTMSS 介导过程的自由基羰基化”Synlett。

Li-Biao Han, Ken-ichi Ishihara, Nobuaki Kambe, Akiya Ogawa, Ilhyong Ryu, Noboru Sonoda: "Carbotelluration of Alkynes" J.Am.Chem.Soc.114. 7591 (1992)

Li-Biao Han、Ken-ichi Ishihara、Nobuaki Kambe、Akiya Okawa、Ilhyong Ryu、Noboru Sonoda：“炔烃的碳化”J.Am.Chem.Soc.114。