Development of 5 Components Coupling Reaction of Dienes

二烯五组分偶联反应的进展

• 批准号: 10650860
• 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: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650860/
• 关键词: π-ally1 complex; nitorosyliron complex; double carbonylation; acylmetallation; 1,3-butadiene; allene; 有機鉄錯体; ジエン化合物

In this study, the aim is development of 5 components coupling reaction. That is, in the presence of alkyl halides and tricarbonylnitrosylferrate, acylmetallation of 1,3-butaienes or 1,2-dienes was discussed and the carbonyl insertion reaction of the resulting iron complexes with 1,2-bis(diphenylphosphino)ethane (DPPE) following the alcoholysis with ethanol was discussed. In the result, the coupling reaction of 5 components of 1,2-dienes or 1,3-butadienes, two molecules of carbon monoxide from tricarbonylnitrosylferrate, alkyl halides, and ethanol completes stereo- and regioselectively.In the presence of tetrabutylammmonium tricarbonylnitrosylferrate (TBAFe), 1,2-dienes (allenes) and alkyl halides reacted to give (η^3-2-acylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of allenes in good yields.In the presence of TBAFe, 1,3-butadienes and alky1 halides reacted to give (η^3-1-acylmethylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of 1,3-butadienes in good yields. The resulting iron complexes reacted with DPPE at the less hindered site of the allylic ligand to give ε-acy1-β, γ-unsaturated acyliron complexes. In succession, the alcoholysis of the acyliron complexes with ethanol gave the corresponding ε-acy1-β, γ-unsaturated carboxylic esters. In a similar manner, (η^3-2-acylally1) dicarbony1-nitrosyliron complexes obtained from 1,2-dienes (allenes) and alky1 halides with TBAFe gave the β-acy1-β, γ-unsaturated acyliron complexes followed by alcoholysis with ethanol to give the β-acy1-β, γ-unsaturated carboxylic esters.

本研究的目的是开发五组分偶联反应，即在烷基卤化物和三羰基亚硝基铁酸盐存在下，讨论 1,3-丁烯或 1,2-二烯的酰基金属化反应以及所得铁的羰基插入反应。讨论了乙醇醇解后与 1,2-双(二苯基膦)乙烷 (DPPE) 的配合物。 1,2-二烯或1,3-丁二烯的5种组分，来自三羰基亚硝基铁酸、烷基卤化物和乙醇的两分子一氧化碳立体选择性和区域选择性地完成。在三羰基亚硝基铁酸四丁基铵(TBAFe)存在下，1,2-二烯(丙二烯)和卤代烷反应得到(η^3-2-酰基1)二羰基亚硝基铁配合物伴随丙二烯的酰基金属化，收率良好。在TBAFe存在下，1,3-丁二烯和烷基卤化物反应生成(η^3-1-酰基甲基烯基1)二羰基亚硝基铁配合物并伴有1,3-丁二烯的酰基金属化反应产率良好。与DPPE在烯丙基配体的受阻较少的位点反应，得到ε-acy1-β，γ-不饱和酰基铁络合物。随后，酰基铁络合物与乙醇醇解，得到相应的ε-酰基1-β，γ-不饱和羧基。以类似的方式，从 1,2-二烯获得 (η^3-2-acylally1) 二羰基 1-亚硝基铁络合物。 （丙二烯）和烷基卤化物与 TBAFe 生成 β-acy1-β, γ-不饱和酰基铁络合物，然后用乙醇醇解生成 β-acy1-β, γ-不饱和羧酸酯。

项目成果

Keiji Itoh,Saburo Nakanishi: "A Route to Functionalized (η^3-Allyl) dicarbonylnitrosyliron Complexes:Regio and Stereoselective Acylmetallation of Allenes"Chemistry Letters.. 2000. 672-673 (2000)

Keiji Itoh、Saburo Nakanishi：“功能化 (η^3-烯丙基) 二羰基亚硝基铁配合物的路线：区域和烯的立体选择性酰基金属化” 化学快报.. 2000. 672-673 (2000)

"A Route to Functionalized (η^3-Ally1) dicarbonylnitrosyliron Complexes : Regio- and Stereoselective Acylmetallation of Allenes"Chemistry Letters, 2000. 672-673 (2000)

“功能化 (η^3-Ally1) 二羰基亚硝基铁络合物的路线：艾伦烯的区域选择性和立体选择性酰基金属化”，化学快报，2000 年。672-673 (2000)