Novel Ruthenium-Catalyzed Synthesis of Polycarboxylic Acid Derivatives

脂肪族和芳香族聚羧酸衍生物在化学工业中都是非常重要的中间体。在本研究中，我们通过交叉偶联反应和环加成反应开发了以下新型的Ru催化的聚羧酸衍生物的合成。首先，通过一种新型的Ru催化的C-C键断裂的环丙烯二聚反应合成了吡喃二酮类化合物。例如，二丙基环丙烯与Ru3(CO)lt；12&gt；和Net_3在四氢呋喃中，在15atm的一氧化碳气氛下，140atm，140atm，反应20h，得到一种新的功能单体3，4，7，8-tetrapropylpyrano[6，5-e]pyran-2，6-dione，，分离收率为81%。在类似的反应条件下，由Ru催化的环丙烯与炔烃的羰基化偶联反应也得到了不对称取代的吡喃二酮。本研究合成的所有吡喃二酮类化合物都是新化合物，由于它们的…，它们作为新型功能单体具有很大的吸引力。更具特色的物理和化学特性。在此基础上，建立了由Cp*RuCl(CoD)/PPh_3[Cp*=五甲基环戊二烯，CoD 1，5-环辛二烯]组成的催化剂体系，用于2位二烷基乙酰二甲酸酯与烯丙基化合物的新型交叉苯环反应。以乙酰二甲酸二甲酯和烯丙醇为原料，在4mol%Cp*RuCl(CoD)和PPh_3存在下，在甲苯中回流反应5h，得到5-甲基-1，2，3，4-苯四甲酸四甲酯，分离收率为84%。此外，在Ru催化剂Cp*RuCl(CoD)的作用下，端炔与二甲基乙酰二甲酸二甲酯进行了高选择性的分子间[2+2+2]环加成反应，直接合成了邻苯二甲酸二甲酯。炔烃和乙酰二甲酸酯的共环三聚反应通常生成1：2的加合物(1，2，3，4-苯四甲酸酯)，而在本反应中，2：1的加合物(邻苯二甲酸酯)是前所未有的主要产物。最近，我们还报道了一种新型的零价[pentacyclo[6.6.0.0^&lt；2，6&gt；.0^&lt；3，13&gt；.0^&lt；10，14&gt；]tetradeca-4，11-diene].-Ru(η^6-cot)(Dmfm)_2，它在2，5-降冰片二烯的二聚反应中表现出了高的催化活性。在进一步研究该配合物的反应活性时，我们发现与对苯二酚反应生成了Ru(η^6-cot)(对苯二酚)配合物，而与芳烃反应生成了新的(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元羧酸衍生物的有效催化剂。较少

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