The Development of A New Intramolecular Cyclization with the Organic Iron Complex

有机铁配合物新型分子内环化的发展

• 批准号: 15550099
• 负责人: ITOH Keiji
• 金额: $ 1.15万
• 依托单位: Osaka Prefectural College of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550099/
• 关键词: Organometallic Complex; Intramolecular Cyclization; Acylmetallation; Iron Complex; ダブルカルボニル化; 有機鉄錯体

In the presence of tetrabutylammonium tricarbonylnitrosylferrate [n-Bu_4N] [Fe(CO)_3NO] (TBAFe), 1,2-dienes (Allenes) reacted with Alkyl halides to give the corresponding (η^3-2-acylallyl) dicarbonylnitorosyliron complexes accompanied with acylmetallation. In this research, we investigate the development of the intramolecular cyclization by the reaction of ω-iodoalkylallenes with TBAFe accompanied with intramolecular acylmetallation as an advancement of the above reaction. ω-Iodoalkylallenes and TBAFe stirred at room temperature under argon for 15 h in dichloromethane and then, the reaction mixtures are chromatographed with silica gel to give the corresponding cyclic (η^3-2-acylallyl)dicarbonylnitrosyliron complexes. The yield of 5 and 6 membered rings are high and that of the 7 membered ring is very low. That of 8 membered ring is lower than that of 5 and 6 membered rings and higher than that of 7 membered ring. Then, the result cyclic π-allyliron complexes react with carbon nucleophiles at room temperature under argon in THF for 15 h. The reaction mixtures are chromatographed with silica gel to give the corresponding 2-alkyl-2-cycloalkenones in good yields. In results, a new synthetic method of some membered ring α,β-unsaturated cyclic enones is developed.

在四丁基三羰基亚硝基铵[n-Bu_4N] [Fe(CO)_3NO] （ttbafe）存在下，1,2-二烯（Allenes）与烷基卤化物反应生成相应的（η^3-2-酰基烯基）二羰基硝基配合物并伴有酰基金属化反应。在本研究中，我们研究了ω-碘烷基烯烯与tafe的分子内环化反应的发展，并作为上述反应的推进，进行了分子内酰基金属化反应。ω-碘烷基亚硝基烯和tafe在室温氩气条件下在二氯甲烷中搅拌15 h，然后用硅胶色谱得到相应的环（η^3-2-酰基烯基）二羰基亚硝基配合物。5元环和6元环的产率较高，7元环的产率很低。8元环比5元和6元环低，比7元环高。然后，将合成的环π-烯丙烯离子配合物与碳亲核试剂在室温氩气条件下反应15 h，用硅胶进行色谱处理，得到相应的2-烷基-2-环烯酮，收率较高。结果，提出了一种合成α，β-不饱和环烯酮的新方法。

项目成果

伊藤詣二, 東田 卓: "π-アリル鉄錯体を経由する分子内環化"日本化学会第4春季年会 2004年 講演予稿集. II. 777 (2004)

Joji Ito、Takashi Higashida：“通过 π-烯丙基铁络合物进行分子内环化”日本化学会 2004 年第四届春季年会论文集。II。