Systemization of Palladium Complex Catalysts and Their Application to Organic Synthesis

本研究的目的是发展钯催化的合成反应，并阐明其反应机理。1.2-丁炔-1，4-二醇衍生物在钯-膦催化剂存在下，在乙醇中进行羰基化反应。以氯甲酸乙酯为碳酸酯，高产率地合成了二(亚甲基)丁二酸酯。2.在乙酸钯和碘的催化下，2-丁炔-1，4-二醇在苯中进行了羰基化反应，得到了光致变色的二硫代黄酮化物。3.钯和铜催化一氧化碳与乙烯或苯乙烯的共聚。裂解-GC分析表明所得聚合物为交替结构。4在中性条件下考察了原核亲核试剂的烯丙化反应、丁二烯的调聚反应和共环化反应。从双π-烯丙基钯中间体的两亲性出发，探讨了它们的反应机理。通过乙烯与卤代芳烃的Heck反应合成了5种苯乙烯类化合物、二苯乙烯类化合物和聚苯乙叉S化合物。

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.