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、烯烃和一氧化碳的共环化，即Pauson-Khand反应，作为选择性有机合成的一种工具越来越受欢迎。我们之前报道了钌配合物催化降冰片烯与炔的[2+环加成反应，其中我们提出了钌环戊烯中间体。如果将一氧化碳插入到真丝环戊烯中，则可以实现催化版的Pauson-Khand反应。经过多次试验，我们终于找到了第一个例子：钌催化的炔与一氧化碳的Pauson-Khand反应。例如，在N， N-二甲基乙酰胺中，在15 atm的一氧化碳压力下，在140℃下，用2 mol%的Ru φ φ D23 φ φ D2(CO) φ φ D212 φ D2处理2-壬烯-3-炔-6,6-羧酸二乙基，得到相应的双环戊烯酮，2-乙基-氧双环[3.3.0]辛-1-烯-7,7-二羧酸二乙基，分离收率为89%。另一方面，在我们努力将目前的反应扩展到分子间版本的Pauso Khand反应中，我们发现了新的钌催化的炔和烯不对称取代氢醌的交叉羰基化反应，其中两分子一氧化碳加入到产物中。例如，在60 atm的一氧化碳和140℃条件下，用2 mol% Ru D23 D2(CO) D212 D2在甲基哌啶中处理20 h，得到相应的对苯二酚4,5-二丙基三环[6.2.1.0 d12,7 D1]十一烷-2(7),3,5-三烯-3,6-二醇，收率为85%。这个反应显然涉及一种马来酰钌中间体，这种中间体是由炔和两分子一氧化碳在铼上反应产生的。总之，这两种反应将在钌催化羰基化反应领域开辟新的化学领域，并分别为制备双环戊烯和非对称取代对苯二酚提供新的实用方法。

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)