Systemization of Palladium Complex Catalysts and Their Application to Organic Synthesis

本研究的目的是发展钯催化合成反应，并阐明其反应机理2-丁烯- 1,4 -二醇衍生物在磷酸氢磷催化剂存在下，在乙醇中羰基化。它的氯甲酸乙酯碳酸盐高产出丁二酸二（亚甲基）噻吩取代的2-丁烯- 1,4 -二醇在乙酸钯和碘的存在下，在苯中羰基化，得到光致变色的二噻吩酰化物研究了钯和铜催化一氧化碳与乙烯或苯乙烯的共聚反应。热解-气相色谱分析表明，所得聚合物具有交替结构在中性条件下研究了亲核原烯丙基化和丁二烯的端粒化和共环化。从双π烯丙基钯中间体的两亲性角度讨论了它们的反应机理以乙烯和卤代芳烃为原料，通过Heck反应合成了苯乙烯、二苯乙烯和聚苯乙烯。

The purpose of the present study was to develop palladium-catalyzed synthetic reactions and to elucidate their reaction mechanisms.1 Derivatives of 2-butyne-1, 4-diol were carbonylated in ethanol in the presence of Pd-phosphine catalyst. Its carbonate of ethyl chloroformate gave bis(methylene)butanedioate in a high yield.2 Thienyl-substituted 2-butyne-1, 4-diols were carbonylated in benzene in the presence of palladium acetate and iodine to give photochromic bisthienylfulgides in one-pot.3 Palladium- and copper-catalyzed copolymerizations of carbon monoxide with ethylene or styrene were investigated. Pyrolysis-GC revealed that the polymers obtained were of alternating structures.4 Allylation of pronucleophiles, and telomerization and cocyclization of buta-diene were investigated under neutral conditions. Their reaction mechanisms were discussed from a viewpoint of amphiphilic nature of the bis-π-allylpalladium intermediate.5 Styrenes, stilbenes, and poly(phenylene vinylene)s were synthesized by the Heck reaction of ethylene with haloarenes.