Development of Catalytic Pauson-Khand Reaction Using Ruthenium Complexes

钌配合物催化 Pauson-Khand 反应的进展

• 批准号: 09650956
• 负责人: KONDO Teruyuki
• 金额: $ 2.18万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650956/
• 关键词: Ruthenium Catalyst; Carbonylation; Pauson-Khand Reaction; Enyne; Alkyne; Alkene; Cyclopentenone; hydroquinone; マレオイル錯体

Metal-mediated cocyclization of alkynes, alkenes and carbon monoxide, the Pauson-Khand reaction, becoming increasingly popular as a tool for selective organic synthesis. We previously reported the [2+cycloaddition of norbornenes with alkynes catalyzed by ruthenium complexes, in which we propose ruthenacyclopentene intermediate. If carbon monoxide is inserted into this ruthenacyclopentene, a cataly version of the Pauson-Khand reaction can be achieved. After many trials, we finally found the first example a ruthenium-catalyzed Pauson-Khand reaction of enynes with carbon monoxide. For example, treatment diethyl 8-nonen-3-yne-6,6-carboxylate with 2 mol% RuィイD23ィエD2(CO)ィイD212ィエD2 in N, N-dimethylacetamide under 15 atm carbon monoxide pressure at 140℃ for 8 h gave the corresponding bicyclic cyclopentenone, diethyl 2-eth3-oxobicyclo[3.3.0]oct-1-ene-7,7-dicarboxylate, in 89% isolated yield.On the other hand, during our effort extend the present reaction to intermolecular version of Pauso Khand reaction, we have found novel rethenium-catalyzed cross-carbonylation of alkynes and alkenes unsymmetrically substituted hydoroquinons, in which two molecules of carbon monoxide were incorporate into the products. For example, treatment of 4-octyne and 2-norbornene with 2 mol% RuィイD23ィエD2(CO)ィイD212ィエD2 in methylpiperidine under 60 atm of carbon monoxide at 140℃ for 20 h gave the corresponding hydroquinor 4,5-dipropyltricyclo[6.2.1.0ィイD12,7ィエD1]undeca-2(7),3,5-triene-3,6-diol, in 85% yield. This reaction apparently involve a maleoylruthenium intermediate which is generated by the reaction of an alkyne and two molecules of carbon monoxide on the rethenium.In coclusion, both reaction will open up new chemistry in the field of ruthenium-catalyzed carbonylation reactions, and offer the novel and practical methods for preparation of bicyclic cyclopentenon and unsymmetically substituted hydroquinones, respectively.

金属介导的炔烃，烷烃和一氧化碳的共生性，Pauson-Khand反应，越来越流行，作为选择性有机合成的工具。我们先前报道了[2+环载细分，氯烯烯由芳基烯酸酯催化的炔烃催化，在其中我们提出了ruthenacyclopentene中间体。如果将碳一氧化碳插入到该芳香苯乙烯中，则可以实现Pauson-Khand反应的催化版本。经过多次试验，我们终于找到了第一个例子，一个含有碳一氧化碳的芬尼催化的pauson-khand反应。例如，用2 mol％RUI D23E D2（CO）D212E D2在N，N-二甲基乙酰氨酰胺下在140 h，N-二甲基乙酰氨酰胺中以140℃的15 h，N-二甲基乙酰氨酰胺在140 h，N-二甲基乙酰胺中处理二乙基8-nonen-3-yne-6-6,6-偶然链酸酯（CO）D23E D2（CO）D212E D2，持续了8 h 2-ETH3-氧气[3.3.0] oct-1-烯-7,7-二羧酸二羧酸盐，以89％的孤立产率。另一方面，在我们的努力中，在我们的努力中，对Pauso Khand反应的分子间版本的呈现反应扩大了反应，我们发现了新型的新型重乙烯菌株，并在两种含有烯烃的烯烃中含有烯烃的交叉含量，并含有烯烃的含量，含有烷基的烯烃，含有烯烃的含量，含有烯烃的含量，含有烯烃的含量，这些均源性含量是烷基的。一氧化碳被纳入产品中。例如，用2 mol％RUI D23E D2（CO）D212E D2在140 h下在60 atm的一氧化碳中处理4-辛烯和2-胞烯烯D2在60 atm的甲基哌啶中，得出相应的氢喹诺4,5-二倍体型[6.2.1.0 d1.1.0 d12,7Ee D1] UNDECA-2（7），3,5-三烯-3,6-二醇，产率为85％。 This reaction apparently involves a maleoylruthenium intermediate which is generated by the reaction of an alcoholne and two molecules of carbon monoxide on the rethenium.In coclusion, both reaction will open up new chemistry in the field of ruthenium-catalyzed carbonylation reactions, and offer the novel and practical methods for preparation of biological cyclopentenon and unsymmetrically substituted氢喹酮分别。

项目成果

Teruyuki Kondo, Nobuyoshi Suzuki, Takumi Okada, Take-aki Mitsudo: "First Ruthenium-Catalyzed Intramolecular Pauson-Khand Reaction"Jounal of the American Chemical Society. 119,no.26. 6187-6188 (1997)

Teruyuki Kondo、Nobuyoshi Suzuki、Takumi Okada、Take-aki Mitsudo：“首次钌催化的 Pauson-Khand 反应”美国化学会杂志。

Take-aki Mitsudo, Nobuyoshi Suzuki, Taka-aki Kobayashi, Teruyuki Kondo: "RuィイD23ィエD2(CO)ィイD212ィエD2/1,10-Phenanthroline-Catalyzed Hydroformylation of Styrene and Acrylic Esters"Journal of Molecular Catalysis A: Chemical. 137,no.1-3. 253-262 (1999)

Take-aki Mitsudo、Nobuyoshi Suzuki、Taka-aki Kobayashi、Teruyuki Kondo：“RuiD23D2(CO)ID212D2/1,10-菲咯啉催化苯乙烯和丙烯酸酯的氢甲酰化”《分子催化杂志 A》137，第 1 期。 -3。253-262（1999）

Teruyuki Kondo: "First Ruthenium-Catalyzed Intramolecular Pauson-Khand Reaction" Journal of the American Chemical Society. 119巻・26号. 6187-6188 (1997)

Teruyuki Kondo：“第一个钌催化的 Pauson-Khand 反应”，美国化学会杂志，第 119 卷，第 26 期。6187-6188 (1997)

Nobuyoshi Suzuki, Teruyuki Kondo, Take-aki Mitsudo: "Novel Ruthenium-Catalyzed Cross-Carbonylation of Alkynes and 2-Norbornenes to Hydroquinones"Organometallics. 17,no.4. 766-769 (1998)

Nobuyoshi Suzuki、Teruyuki Kondo、Take-aki Mitsudo：“新型钌催化的炔烃和 2-降冰片烯到氢醌的交叉羰基化”有机金属化合物。

Teruyuki Kondo: "Novel Ruthenium-Complex-Catalyzed Synthesis of Ureas from Formamides and Amines" Organometallics. 16巻・12号. 2562-2670 (1997)

Teruyuki Kondo：“新型钌复合物催化从甲酰胺和胺合成脲”有机金属学，第 16 卷，第 12 期。2562-2670 (1997)