Ruthenium Complex-Catalyzed Highly Selective Organic Syntheses

钌配合物催化的高选择性有机合成

• 批准号: 05403024
• 负责人: WATANABE Yoshihisa
• 金额: $ 21.57万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05403024/
• 关键词: Ruthenium complex; Selective organic synthesis; pi-Allylruthenium complex; Ambiphilicity; Formyl C-H activation; Carbonylation; Organometallic catalysis; Reductive N-Heterocyclization; 還元的N-複素環化反応; 炭素-炭素結合生成反応; アリル化反応; 炭素求核剤; アセチレン; ノルボルネン

We have been studying on ruthenium complex-catalyzed novel selective organic syntheses, especially from the view point of novel and selective carbon-carbon bond forming reactions. In the present work, ruthenium complex catalyzed novel methods for construction of carbon skeleton via pi-allylruthenium complexes as key intermediates or formyl C-H bond activation, together with the selective organic syntheses using related transition metal complex catalysts, have been developed. This year, 1. we have found that several eta^3-allylruthenium (II) complexes, such as (eta^3-allyl) Ru (OAc) (CO)_3 or cationic (eta^3-allyl) Ru (CO)_3] ^+ (OTf)^-, can function as both a nucleophile and an electrophile, i.e., as an ambiphile. 2. The following ruthenium complex-catalyzed novel transformations of alkyl formates were developed : selective decarbonylation of alkyl formates to alcohols, alkylation of arenes and alkenes using alkyl formates in neutral media, and addition of alcohols to alkenes. 3. Photo-, electro-, and thermal carbonylation of alkyl iodides in the presence of group 7 and 8-10 metal carbonyl catalysts, including ruthenium complexes. 4. In the course of the study on ruthenium complex-catalyzed reactions, we have found that Co_2 (CO)_8-catalyzed ring-opening carbonylation of oxiranes and oxetane smoothly proceeds with high regioselectivity under 1 atm of carbon monoxide at room temperature to give the corresponding beta- and gamma-siloxyamides in high yields, respectively. In addition, the PdCl_2 (PPh_3)_2-SnCl_2 system was found to show high catalytic activity for the reductive N-heterocyclization of nitrobenzenes to indole and 2H-indazole derivatives. The intermolecular reductive N-heterocyclization of 2-nitrobenzaldehyde or 2-nitrophenyl ketones with formamide using PdCl_2 (PPh_3)_2 with MoCl_5 was found to give the corresponding quinazoline derivatives in moderate yields.

我们一直在研究钌配合物催化的新型选择性有机合成，特别是从新型和选择性的碳-碳键形成反应的角度。本论文研究了以π-烯丙基钌配合物为关键中间体或以甲酰基C-H键为活化剂的钌配合物催化构建碳骨架的新方法，以及利用相关过渡金属配合物催化剂进行的选择性有机合成。今年，1。我们已经发现，几种η ^3-烯丙基钌（II）络合物，例如（η ^3-烯丙基）Ru（OAc）（CO）_3或阳离子（η ^3-烯丙基）Ru（CO）_3] ^+（OTf）^-，可以同时起到亲核试剂和亲电试剂的作用，即，一个模棱两可的人2.本文报道了钌络合物催化的甲酸烷基酯的新型转化反应：甲酸烷基酯选择性脱羰生成醇，甲酸烷基酯在中性介质中进行芳烃和烯烃的烷基化反应，以及醇与烯烃的加成反应。3.在第7和8-10族金属羰基催化剂（包括钌络合物）存在下，烷基碘的光、电和热羰基化。4.在钌络合物催化反应的研究过程中，我们发现在室温下，1个大气压的CO存在下，Co_2（CO）_8催化的环氧乙烷和氧杂环丁烷的开环羰基化反应顺利进行，并具有高的区域选择性，分别高产率地得到相应的β-和γ-乙酰胺。此外，PdCl_2（PPh_3）_2-SnCl_2体系对硝基苯类化合物的还原N-杂环化反应也表现出很高的催化活性。用PdCl_2（PPh_3）_2和MoCl_5催化2-硝基苯甲醛或2-硝基苯酮与甲酰胺的分子间还原性N-杂环化反应，以中等产率得到相应的喹唑啉衍生物。

项目成果

Motohiro Akazome: "Complex-Catalyzed Reductive N-Heterocyclization of Nitroarenes:Novel Synthesis of Indole and 2H-Indazole Derivatives" J.Org.Chem.59. 3375-3380 (1994)

Motohiro Akazome：“硝基芳烃的复合催化还原 N-杂环化：吲哚和 2H-吲唑衍生物的新合成”J.Org.Chem.59。

Teruyuki Kondo: "Ruthenium Complex-Catalyzed Novel Transformation of Alkyl Formates" J.Organomet.Chem.(in press.).

Teruyuki Kondo：“钌配合物催化烷基甲酸盐的新型转化”J.Organomet.Chem.（正在印刷中）。

Yoshihisa Watanabe: "Co_2(CO)_8-Catalyzed Ring-Opening Carbonylation of Cyclic Ethers Using N-Silylamines" Bull.Chem.Soc.Jpn.67. 879-882 (1994)

Yoshihisa Watanabe：“使用 N-甲硅烷基胺的 Co_2(CO)_8 催化环状醚的开环羰基化”Bull.Chem.Soc.Jpn.67。

Teruyuki Kondo: "Nucleophilic and Electrophilic Allylation Reactions.Synthesis,Structure and Ambiphilic Reactivity of η3-Allylruthenium(II)Complexes" Organometallics. (印刷中). (1995)

Teruyuki Kondo：“亲核和亲电烯丙基化反应。η3-烯丙基钌 (II) 配合物的合成、结构和两性反应性”有机金属学（出版中）。

Motohiro Akazome: "Complex-Catalyzed Reductive N-Heterocyclization of Nitroarenes : Novel Synthesis of Indole and 2H-Indazole Derivatives" J.Org.Chem.vol.59. 3375-3380 (1994)

Motohiro Akazome：“硝基芳烃的复合催化还原 N-杂环化：吲哚和 2H-吲唑衍生物的新合成”J.Org.Chem.vol.59。