Systemization of Palladium Complex Catalysts and Their Application to Organic Synthesis

钯配合物催化剂的体系化及其在有机合成中的应用

• 批准号: 09650962
• 负责人: KIJI Jitsuo
• 金额: $ 2.18万
• 依托单位: Tottori 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 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650962/
• 关键词: Palladium catalyst; Carbonylation; Olefin-CO copolymerization; Bis-π-allylpalladium; クロスカップリング; Hedk反応; ブタジエンの環化付加

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.

本研究的目的是开发钯催化的合成反应并阐明其反应机理。1在钯膦催化剂的存在下，在乙醇中对2-丁炔-1，4-二醇衍生物进行羰基化反应。2噻吩基取代的2-丁炔-1，4-二醇在乙酸钯和碘存在下，在苯中一锅法羰基化合成了光致变色的双噻吩基俘精酸酐。3研究了钯和铜催化一氧化碳与乙烯或苯乙烯的共聚反应。热裂解-气相色谱分析表明，所得聚合物具有交替结构。4在中性条件下，研究了亲核试剂的烯丙基化反应、丁二烯的调聚和共环化反应。从双-π-烯丙基钯中间体的两亲性的观点讨论了它们的反应机理。5通过乙烯与卤代芳烃的Heck反应合成了苯乙烯、均二苯乙烯和聚苯撑乙烯。

项目成果

Yasushi Yokoyama: "Highly Diastereoselective Photochromic Cyclization of a Bismethylenethienylfulgide"Chem. Lett.. (印刷中). (2000)

Yasushi Yokoyama：“双亚甲基噻吩基俘酰酸的高度非对映选择性光致变色环化”Chem.Lett.（出版中）。

J.Kiji: "Alternating Olefin-Carbon Monoxide Copolymers and Their Derivatives" J.Anal.Appl.Pyrolysis. 40-41. 331-345 (1997)

J.Kiji：“交替烯烃-一氧化碳共聚物及其衍生物”J.Anal.Appl.Pyrothesis。

Jitsuo Kiji: "Palladium-Catalyzed Arylation of Ethylene"J. Mol. Catal.. 147. 3-10 (1999)

Jitsuo Kiji：“钯催化的乙烯芳基化”J。

木地実夫: "有機工業化学 そのエッセンス(分担執筆)"裳華房. 313 (1999)

Saneo Kiji：“有机工业化学的本质（合著者）”Shokabo 313（1999）。

J.Kiji, T.Okano, H.Kimura, K.Saiki: "Palladium-catalyzed Carbonylative Coupling of Iodobenzene and 2-Methyl-3-butyn-2-ol under Biphasic Conditions" J.Mol.Catal.A : Chem.130. 95-100 (1998)

J.Kiji、T.Okano、H.Kimura、K.Saiki：“双相条件下碘苯和 2-甲基-3-丁炔-2-醇的钯催化羰基化偶联”J.Mol.Catal.A：Chem。