実践的有機金属反応剤の開発と天然物指向有機合成への新展開

实用有机金属试剂开发及天然产物有机合成新进展

• 批准号: 09231206
• 负责人: 細見 彰
• 金额: $ 1.41万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 无数据
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-09231206/
• 关键词: 1,3-双極子; 立体選択的合成; カルボニルイリド; 還元的メタル化; ラジカル反応; サマリウム推進反応; テトラヒドロフラン; ケイ素誘導反応

多官能性有機金属化合物の合成設計と新反応およびその合成化学への応用を目指した研究の一環として,(1)合成化学的に重要であるが反応性が高いために十分に活用されていない反応活性種である有機ラジカルを用いるあたらしい.立体選択的な有機合成反応を見つけた.ラジカル開始剤存在下アルケンとアリルスタナンを反応させれば,スタニルラジカルのアルケンへの付加および生成するアルキルラジカルのアリル化により,ラジカル的アリルスタニル化の初めての例を見つけた. さらに、アルキンとの反応においてもアリルスタニル化が効率的にかつこう立体選択的に進行することを見つけた。(2)サマリウムを用いる新反応を開発する目的で非安定化カルボニルイリドの生成と新規反応を見つけた.ビス(クロロメチルエーテル)に2価サマリウムを作用させることによりカルボニルイリドが生成し,カルボニル化合物存在下に行うとジオキソランが,また,アルケン類およびアルキン類共存下では高収率で対応するテトラヒドロフラン類とジヒドロフラン類が生成することを見つけた.本反応により世界で始めて全く置換基を持たない母体のカルボニルイリドを得ることができたばかりでなく,"Taior-made" のカルボニルイリドを自由に得る方法を明らかにできた.(3)有機マンガンアート錯体を新規電子移動型還元剤として用いるアリル銅種およびマンガンエノラートの新規生成反応を見つけた.(4)分子内の適当な位置に水酸基のような求核剤を有するビニルシランを用いたところ,プロトンやLewis酸触媒による反応によって生じるβ-シリル炭素陽イオン中間体が,1,2-ケイ素転移を伴い,水酸基と反応して,テトラヒドロフランやテトラヒドロピラン誘導体などの含酸素環状化合物を立体選択的に効率よく与えることを見つけた.

Multi-functional organic metal compound synthesis design new anti-organic synthetic chemistry laboratory using target indicator to study one of the most important chemical reactions in synthetic chemistry. (1) the most important anti-organic metal compounds in synthetic chemistry are very active in the use of anti-organic chemicals. Stereoscopically selected machine-based synthesis of anti-filtering systems. At the beginning of the system, there is a general situation in which there is a negative response, which is caused by the increase in the number of payments. in the beginning, there is a general situation in which there is an increase in the number of payments. at the beginning of the system, there is an increase in the number of payments. in the beginning of the system, there is a general situation. In order to improve the accuracy of the stereoscopic selection of the conversion rate, there is a significant difference between the two groups. (2) for the purpose of non-stabilization, new laws and regulations will be generated. In the presence of a variety of compounds, such as the presence of a variety of compounds, the presence of a variety of compounds in the presence of the same type of coexistence. in the presence of a variety of compounds, the presence of a variety of compounds in the presence of the same type of coexistence. in the presence of the same type of coexistence, there are significant differences between the two groups. At the beginning of this anti-world policy, we have a complete set of information on the basis of the parent system. "Taior-made" is used to obtain information about the free access method. (3) there is an opportunity to change the number of devices in the system. (3) there is an opportunity to generate new rules for electronic mobility by using a variety of new rules. (4) the intramolecular molecular weight is located in the aqueous acid base to obtain the nuclear response. I don't know how to use it. In this paper, the effect of Lewis acid catalyst on the production of β-carboxylic acid, acid-based acid, acid-based acid, acid-containing environmental compounds, acid-containing compounds, acid-containing environmental compounds, acid-containing compounds

项目成果

A.Hosomi: "New Access to Cross-Coupling Reaction between Arylsilanes or Heteroarylsilanes and Aryl Halides Mediated by a Copper(I) Salt" Chem.Lett.,. 7. 639-640 (1997)

A.Hosomi：“通过铜（I）盐介导的芳基硅烷或杂芳基硅烷与芳基卤化物之间交叉偶联反应的新途径”Chem.Lett.，。

A.HOSOMI: "A New Type of Allyl-and Prop-2-ynyl-manganese Species: Generation and Reactions with Electrophiles" J.Chem.Soc.,Chem.Commun.,. 21. 2077-2078 (1997)

A.HOSOMI：“新型烯丙基-和丙-2-炔基-锰物种：生成及其与亲电试剂的反应”J.Chem.Soc.，Chem.Commun.，。

A.Hosomi: "Manganese Ate Complexes as New Reducing Agents : Perfectly Regiocontrolled Generation and Reaction of the Manganese Enolates with Electrophiles" J.Am.Chen.Soc.,. 119・23. 5459-5460 (1997)

A.Hosomi：“作为新还原剂的锰酸配合物：锰烯醇化物与亲电试剂的完美区域控制生成和反应”J.Am.Chen.Soc.，119・23（1997）。

A.Hosomi: "A New and Mild System for the Generation of Nonstabilized Carbonyl Ylides:Synthetically Practical Ues in the Reactions with Electron-Deficient Dipolarophiles" J.Org.Chem.,. 62・25. 8610-8611 (1997)

A.Hosomi：“用于生成不稳定羰基叶立德的新型温和系统：在缺电子偶极亲和物反应中的合成实用”J.Org.Chem., 8610-8611 (1997)。

A.Hosomi: "Generation of a Reducing Reagent from Copper (I) Salt and Hydrosilane. New Pratical Method for Conjugate Reduction" Tetrahedron Lett.,. 38・51. 8887-8890 (1997)

A.Hosomi：“从铜 (I) 盐和氢硅烷生成还原剂。共轭还原的新实用方法”Tetrahedron Lett., 8887-8890 (1997)。