Development of Novel Synthetic Reactions Utilizing Transition-Metal Complexes Containing Carbon-Metal Multiple Bonds

利用含有碳-金属多重键的过渡金属配合物开发新型合成反应

• 批准号: 12440176
• 负责人: IWASAWA Nobuharu
• 金额: $ 9.66万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440176/
• 关键词: vinylidene complex; carbene complex; one-electron reduction; benzopyranylidene complex; metal-containing carbonyl ylide; polycyclic indole; tungstencarbonyl complex; タングステンカルボニル; 6-シロキシ-5-エン-1-イン; 6-シロキシ-1,2,5-トリエン; 1,2-ジエンの求電子的活性化; シクロペンテン環形成反

This research has focused on the development of novel carbon-carbon bond forming reactions utilizing the transition metal complexes containing carbon-metal multiple bonds.1) Two types of novel reactive species were generated by one-electron reduction of Fischer-type carbene complexes. In the case of tungsten complexes, one-electron reduction generated anion radical species, which added to electron-deficient olefins to give addition products. In the case of chromium complexes, carbonyl insertion occurred to give acyl chromate complexes, which underwent 1, 4-addition to various electron-deficient olefins.2) Treatment of o-ethynylphenylketone derivatives with W(CO_5・THF gave novel benzopyranylidene complexes through electrocyclization of vinylidene intermediates. These complexes readily underwent inverse electron demand Diels-Alder reaction with electron-rich olefins to give naphthalene derivatives in good yield. Furthermore, we have developed a novel method for the generation of metal-containing carbonyl ylides by the reaction of o-ethynylphenyl ketones with W(CO)_5・THF. The [3+2]-cycloaddition of these ylides with electron-rich alkenes followed by insertion of the resulting tungsten carbene moiety into a neighboring C-H bond realizes the construction of complex cyclic carbon frameworks in a single step. This reaction was further developed into a novel method for the synthesis of polycyclic indole derivatives through the generation of metal-containing azomethine ylides.3) Treatment of ω-acetylenic silyl enol ethers with a catalytic amount of W(CO)_5・L realizes an effective electrophilic activation of the acetylenic moiety for the attack of the silyl enol ether part to give cyclized products in high yield. This reaction has been studied extensively and a variety of synthetically useful reactions have been developed.

本研究的重点是利用含有碳-金属多重键的过渡金属配合物开发新型碳-碳键形成反应。1）费舍尔型卡宾配合物的单电子还原产生了两种新型反应物种。在钨配合物的情况下，单电子还原产生的阴离子自由基物种，它添加到缺电子的烯烃，得到加成产物。2）邻乙炔基苯基酮衍生物与W（CO_5·THF）反应，通过亚乙烯基中间体的电环化反应，得到了新的苯并吡喃亚甲基配合物。这些配合物容易与富电子烯烃发生反电子需求Diels-Alder反应，以良好的产率得到萘衍生物。此外，我们还发展了一种由邻乙炔基苯基酮与W（CO）_5·THF反应生成含金属羰基叶立德的新方法。这些叶立德与富电子烯烃的[3+2]-环加成，然后将所得的钨卡宾部分插入到相邻的C-H键中，实现了在单一步骤中构建复杂的环状碳框架。3）催化量的W（CO）_5·L处理ω-炔基硅烯醇醚，可有效地活化炔基，进攻硅烯醇醚部分，高产率地得到环化产物。该反应已被广泛研究，并已开发出各种合成有用的反应。

项目成果

N.Iwasawa: "Novel Synthesis of Pentacarbonylbenzopyranylidenetungsten(0) Complexes and their Diels-Alder Reaction with Electron-Rich Alkenes"J.Am.Chem.Soc.. 122. 10226-10227 (2000)

N.Iwasawa：“五羰基苯并吡喃基钨(0)配合物的新合成及其与富电子烯烃的狄尔斯-阿尔德反应”J.Am.Chem.Soc.. 122. 10226-10227 (2000)

T.Miura: "Reactions of Iodinated Vinylidene Complexes Generated from 1-Iodo-1-alkynes and W(CO)_5(thf)"J.Am.Chem.Soc.. 124. 518-519 (2002)

T.Miura：“1-Iodo-1-alkynes 和 W(CO)_5(thf) 生成的碘化亚乙烯基配合物的反应”J.Am.Chem.Soc.. 124. 518-519 (2002)

T.Miura, N.Iwasawa: "Reactions of lodinated Vinylidene Complexes Generated from 1-Iodo-1-alkynes and W(CO)_5・THF"J. Am. Chem. Soc. 124. 518-519 (2002)

T. Miura, N. Iwasawa：“由 1-Iodo-1-alkynes 和 W(CO)_5·THF 生成的碘化亚乙烯基配合物的反应”J. Am. 124. 518-519 (2002)

T.Miura: "W(CO)_5(L)-Catalyzed Endo-Selective Cyclization of Allenyl Silyl Enol Ethers : An Efficient Method for the Cyclopentene Annulation onto α,β-Unsaturated Ketones"Org.Lett.. 5. 1725-1728 (2003)

T.Miura：“W(CO)_5(L)-催化烯基甲硅烷基烯醇醚的内选择性环化：环戊烯环化到 α,β-不饱和酮上的有效方法”Org.Lett.. 5. 1725-1728 (2003)

N.Iwasawa, T.Miura, K.Kiyota, H.Kusama, K.Lee, P.H.Lee: "An Efficient Method for the Cyclopentene Annulation onto α,β-Unsaturated Ketones : W(CO)_5(L) Catalyzed 5-Endo-Dig Cyclization of 6-Siloxy-5-en-1-"Org.Lett.. 4. 4463-4466 (2002)

N.Iwasawa、T.Miura、K.Kiyota、H.Kusama、K.Lee、P.H.Lee：“环戊烯成环到 α,β-不饱和酮上的有效方法：W(CO)_5(L) 催化 5- 6-Siloxy-5-en-1-"Org.Lett.. 4. 4463-4466 (2002) 的 Endo-Dig 环化