Steric Control of Reactive Transition Meal Species

反应性过渡粉物质的空间控制

• 批准号: 10208210
• 负责人: CHATANI Naoto
• 金额: $ 6.91万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10208210/
• 关键词: Carbon Monoxide; Cycloaddition; Carbonylation; Ketone; Lactone; Coupling; Alkene; 環化カップリング; イミン; ラクタム; ルテニウム; 環化付加; シクロカルボニル化; 環化異性化; 触媒; 遷移金属; 環化反応; 多環状化合物; 環化カルボニル化

Transition-metal-catalyzed cycloaddition reactions have clearly been demonstrated to be a powerful tool in organic synthesis. A variety of ring systems can be constructed via transition metal-catalyzed cycloaddition reactions. If one uses carbon monoxide (CO) as one carbon unit, one can expect to get carbocyclic or heterocyclic carbonyl compounds from simple acyclic building blocks. The purpose of the present study was the development of new type of carbonylative cycloaddition reactions using aldehyde (or ketone) π-bond as two-atom unit.Several new types of carbonylative cycloaddition reactions, as shown below was found. In all cases, Ru_3(CO)_<12> was a catalyst of choice. (1) intramolecular [2+2+1]cycloaddition of aldehydes, alkynes, and CO; (2) [4+1]cycloaddition of α,β-unsaturated imines and CO; (3) intermolecular [2+2+1]cycloaddition of ketones (aldehydes), alkenes (alkynes), and CO.In the reaction 3, simple aldehydes (or ketones) did not serve as the substrate, however a wide variety of ketones, such as α-dicarbonyl compounds and N-heterocyclic ketones, can be used in this cycloaddition. A high diastereoselectivity was observed when pyridylmethyl ketone was used as the substrate and cyclopentene was used as an olefin component.

过渡金属催化的环加成反应已被证明是有机合成的有力工具。通过过渡金属催化的环加成反应可以构建多种环系。如果一个人使用一氧化碳(CO)作为一个碳单元，人们可以预期从简单的非环构建块得到碳环或杂环羰基化合物。本研究的目的是开发以醛(酮)π-键为两原子单元的新型羰基环加成反应。在所有情况下，Ru_3(CO)_12都是催化剂的选择。(1)醛、炔和CO的分子内[2+2+1]环加成反应；(2)α，β-不饱和亚胺和CO的[4+1]环加成反应；(3)酮(醛)、烯(炔)和CO的分子间[2+2+1]环加成反应。在反应3中，不以简单的醛(或酮)为底物，但可以使用多种酮，如α-二酮化合物和N-杂环酮。以吡啶甲基酮为底物，环戊烯为烯烃组分时，有较高的非对映选择性。

项目成果

Naoto Chatani: "Ruthenium Carbonyl-Catalyzed [2+2+1]Cycloaddition of Ketones, Olefins, and Carbon Monoxide Leading to Functionalized γ-Butyrolactones"J. Am. Chem. Soc.. 121(30). 7160-7161 (1999)

Naoto Chatani：“钌羰基催化的酮、烯烃和一氧化碳的环加成反应生成官能化 γ-丁内酯”J. Am. 121(30)。 ）

Naoto Chatani: "Ruthenium Carbonyl-Catalyzed[2+2+1]Cycloaddition of Ketones,Olefins,and Carbon Monoxide Leading to Functionalized γ-Butyrolactones"J.Am.Chem.Soc.. 121. 7160-7161 (1999)

Naoto Chatani：“钌羰基催化[2+2+1]酮、烯烃和一氧化碳的环加成反应生成官能化 γ-丁内酯”J.Am.Chem.Soc.. 121. 7160-7161 (1999)

Naoto Chatani: "Ru_3(CO)_<12>-Catalyzed Intermolecular Cyclocoupling of Ketones,Alkenes or Alkynes,and Carbon Monoxide. [2+2+1]Cycloaddition Strategy for the Synthesis of Functionalized γ-Butyrolactones"J.Am.Chem.Soc.. 122. 12663-12674 (2000)

Naoto Chatani：“Ru_3(CO)_<12>-催化酮、烯烃或炔烃和一氧化碳的分子间环偶联。用于合成功能化 γ-丁内酯的[2+2+1]环加成策略”J.Am.Chem .社会.. 122. 12663-12674 (2000)

Naoto Chatani: "The Ru_3(CO)_<12>-Catalyzed Intermolecular [2+2+1] Cyclocoupling of Imines, Alkenes or Alkynes, and Carbon Monoxide : A New Synthesis of Functionalized γ-Lactames"Synthesis. (7). 925-928 (2000)

Naoto Chatani：“Ru_3(CO)_12-催化的亚胺、烯烃或炔烃和一氧化碳的分子间[2+2+1]环偶联：功能化γ-内酰胺的新合成”(7)。 925-928 (2000)

茶谷直人: "Construction of Novel Polyclic Ring Systems by Transition-Metal-Catalyzed Cycloisomerization of Ene-Ene-Yhes" J.Am.Chem.Soc.120・35. 9104-9105 (1998)

Naoto Chatani：“通过过渡金属催化的 Ene-Ene-Yhes 环异构化构建新型多环体系”J.Am.Chem.Soc.120・35（1998）。