Novel Ruthenium-Catalyzed Synthesis of Polycarboxylic Acid Derivatives

新型钌催化聚羧酸衍生物的合成

• 批准号: 13555246
• 负责人: MITSUDO Take-aki
• 金额: $ 8.7万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555246/
• 关键词: Ruthenium catalyst; Allylic alcohols; Alkyne; Benzannulation; o-Phthalic acid; Acrylates; Origomerization; Norbornene; メタラサイクル; [2+2+2]付加環化反応; o-フタル酸エステル; 二量化反応; 2-ノルボルネン; カルボニル化反応; 付加環化反応; 炭素-炭素結合切断; シクロプロペノン; )アリルアルコール; ピラノピランジオン; ベンゼ

Both aliphatic and aromatic polycarboxylic acid derivatives are highly important intermediates in chemical industry. In this study, we developed the following novel ruthenium-catalyzed syntheses of polycarboxilic acid derivatives involving cross-coupling and cycloaddition reactions. First, pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru_3(CO)_<12> and NEt_3 in THF under 15 atm of carbon monoxide at 140℃ for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions. All pyranopyrandiones prepared in this study are new compounds, which are quite attractive as novel functional monomers due to their … More characteristic physical and chemical properties. Then, a catalyst system consisting, of Cp*RuCl(cod)/PPh_3 [Cp* = pentamethylcyclopentadienyl, cod 1,5-cyclooctadiene] for the novel cross-benzannulation of 2 equip of dialkyl acetylenedicarboxylate with an allylic compound has been developed. As an example, the reaction of dimethyl acetylenedicarboxylate with allyl alcohol in the presence of 4 mol % Cp*RuCl(cod) and PPh_3 under reflux in toluene for 5 h gave tetramethyl 5-methyl-1,2,3,4-benzenetetracarboxylate in an isolated yield of 84%. Furthermore, a highly chemoselective intermolecular [2 + 2 + 2] cycloaddition of 2 eqiv of terminal alkynes with dimethyl acetylenedicarboxylate, which enables the straightforward synthesis of dialkylated o-phthalates, was successfully accomplished using a ruthenium catalyst, Cp*RuCl(cod). The co-cyclotrimerization of alkynes and acetylenedicarboxylates usually affords 1:2 adducts (1,2,3,4-benzenetetracarboxylates), however, in the present reaction 2:1 adducts (o-phthalates) are the major products unprecedentedly. Recently, we have also reported the novel zerovalent ruthenium complex Ru(η^6-cot)(dmfm)_2, which showed high catalytic activity in a unique dimerization of 2,5-norbornadiene to novel half-cage compounds, PCTD [pentacyclo[6.6.0.0^<2,6>.0^<3,13>.0^<10,14>]tetradeca-4,11-diene]. During our further investigation of the reactivity of this complex, we found that the reaction with p-quinones gave Ru(η^6-cot)(p-quinone) complexes, while the reaction with arenes gave novel (η^6-arene)Ru(dmfm)_2 complex. All reactionsproceeded via the direct ligand exchange reactions of cot and/or dmfm in Ru(η^6-cot)(dmfm)_2, and the new complexes prepa-red here can be expected as efficient catalysts for the synthesis of aliphatic and aromatic polycarboxylic acid derivatives. Less

脂肪族和芳香族多元羧酸衍生物是重要的化工中间体。在本研究中，我们发展了下列新颖的多羧酸衍生物的合成，包括交叉偶联和环加成反应。首先，通过一种新的环丙烯酮的羰基化二聚反应，通过C-C键的断裂制备了吡喃并吡喃二酮。例如，二丙基环丙烯酮与催化量的Ru_3（CO）_3<12>和NEt_3在THF中于15 atm一氧化碳和140℃反应20 h，得到一种新的功能单体3，4，7，8-四丙基吡喃并[6，5-e]吡喃-2，6-二酮，分离收率为81%。在类似的反应条件下，环丙烯酮与炔的羰基化偶联反应也得到了不对称取代的吡喃并吡喃二酮。本研究中所合成的吡喃并吡喃二酮均为新化合物，由于其结构简单，是一类很有吸引力的新型功能单体。 ...更多信息 物理和化学特性。在此基础上，研究了Cp ~*RuCl（cod）/PPh_3 [Cp ~* =五甲基环戊二烯，cod 1，5-环戊二烯]催化体系对炔二甲酸二烷基酯与烯丙基化合物的新型交叉苯并环化反应的催化性能。以乙炔二甲酸二甲酯和烯丙醇为例，在4mol%Cp *RuCl（cod）和PPh_3存在下，甲苯中回流反应5 h，得到5-甲基-1，2，3，4-苯四甲酸四甲酯，分离收率为84%。此外，使用钌催化剂Cp*RuCl（cod）成功地实现了2当量末端炔与乙炔二甲酸二甲酯的高化学选择性分子间[2 + 2 + 2]环加成，这使得能够直接合成二烷基化邻苯二甲酸酯。炔和炔二羧酸酯的共环三聚反应通常得到1：2的加成物（1，2，3，4-苯四羧酸酯），而在本反应中，2：1的加成物（邻苯二甲酸酯）是前所未有的主要产物。最近，我们还报道了新型零价钌配合物Ru（η^6-cot）（dmfm）_2，它在2，5-降冰片二烯独特的二聚反应中表现出高催化活性，生成新型半笼化合物PCTD [pentacyclo[6.6.0.0 ^&lt;2，6&gt;.0^&lt;3，13&gt;.0^&lt;10，14&gt;]十四碳-4，11-二烯]。在进一步研究配合物的反应活性时，我们发现与对苯醌反应得到Ru（η^6-cot）（对苯醌）配合物，与芳烃反应得到新的（η^6-芳烃）Ru（dmfm）_2配合物。所有反应都是通过cot和/或dmfm在Ru（η^6-cot）（dmfm）_2中的直接配体交换反应进行的，这些新的配合物有望成为合成脂肪族和芳香族多羧酸衍生物的有效催化剂。少

项目成果

Yasuyuki Ura: "Synthesis of Novel Zerovalent Ruthenium η^6-Arene Complexes via Direct Displacement of a 1,3,5-Cyclooctatriene Ligand by Arenes"Organometallics. 22・9. 1863-1867 (2003)

Yasuyuki Ura：“通过芳烃直接置换 1,3,5-环辛三烯配体合成新型零价钌 η^6-芳烃配合物”有机金属学 1863-1867。

Teruyuki Kondo, Yushi Kaneko, Yoshinori Taguchi, Ayako Nakamura, Takumi Okada, Masashi Shiotsuki, Yasuyuki Ura, Kenji Wada, Take-aki Mitsudo: "Rapid Ruthenium-Catalyzed Synthesis of Pyranopyrandions by Reconstructive Carbonylation of Cyclopropenones Invol

Teruyuki Kondo、Yushi Kaneko、Yoshinori Taguchi、Ayako Nakamura、Takumi Okada、Masashi Shiotsuki、Yasuyuki Ura、Kenji Wada、Take-aki Mitsudo：“通过环丙烯酮的重构羰基化快速钌催化合成吡喃吡喃酮

Teruyuki Kondo: "Novel Synthesis of Benzenepolycarboxylates by Ruthenium-Catalyzed Cross-Benzannulation of Acetylenedicarboxylates with Allylic Compounds"Organometallics. 21・21. 4564-4567 (2002)

Teruyuki Kondo：“钌催化乙炔二羧酸酯与烯丙基化合物的苯多羧酸酯的新合成”有机金属学 21・21（2002）。

Take-aki Mitsudo, Teruyuki Kondo: "Ruthenium Complex-Catalyzed Formation and Cleavage of Carbon-Carbon σ-Bonds. On the Requirement of Highly Qualified Tuning of the Reaction Conditions"Synlett. No.3. 309-321 (2001)

Take-aki Mitsudo、Teruyuki Kondo：“钌配合物催化的碳-碳 σ-键的形成和裂解。关于反应条件的高质量调整的要求”Synlett No.309-321。

Yasuyuki Ura, Yoshitaka Sato, Masashi Shiotsuki, TeruyukiKondo, Take-aki Mitsudo: "Ruthenium-Catalyzed Synthesis of o-Phthalates by Highly Chemoselective Intermolecular [2 + 2 + 2] Cycloaddition of Terminal Alkynes and Dimethyl Acetylenedicarboxylate"J.Mo

Yasuyuki Ura、Yoshitaka Sato、Masashi Shiotsuki、Teruyuki Kondo、Take-aki Mitsudo：“通过末端炔烃和乙炔二甲酸二甲酯的高化学选择性分子间[2 2 2]环加成反应，钌催化合成邻苯二甲酸酯”J.Mo