Biphasic Reaction by Palladium Catalyst

钯催化剂的双相反应

• 批准号: 07651059
• 负责人: KIJI Jitsuo
• 金额: $ 1.34万
• 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: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651059/
• 关键词: Palladium catalyst; Carbonylation; Biphasic reaction; Allylic compound; Heck reaction; アルケニルケトン; ブテノリド; フラノン

One serlous probelm of homogeneous catalyst is the separation of the product from the catalyst. Since the hydroformylation of propene under biphasic conditions was commercialized in 1984, two-phase catalysis by transition metal complexes attracts much attention. In the present study carbonylation and the Heck reaction were carried out using Pd/water-soluble phosphine or Pd/triphenylphosphine/phase transfer agent as the catalyst.1 Carbonylation of allylic halidesPalladium-catalyzed, atmospheric pressure carbonylation of allylic halides under alcohol-potassium carbonate two-phase conditions affords beta, gamma-unsaturated esters.2 Carbonylative coupling of iodobenzene and propargyl alcoholThe reaction of iodobenzene with 2-methyl-3-butyn-2-ol under aqueous NaOH affords a butenolide in one-pot by successive reactions of carbonylation, reduction, and cyclocarbonylation. It was clarified that the biphasic reaction is a contrast to the homogeneous one.3 Arylation of ethyleneThe arylation of ethylene with aryl halides by phosphine-modified palladium catalysts takes place readily to afford stirenes. A variety of functional monomers were synthesized by this methods.

均相催化剂的一个严重问题是产物与催化剂的分离。自1984年丙烯两相氢甲酰化工业化以来，过渡金属络合物的两相催化反应引起了人们的广泛关注。在本研究中，以Pd/水溶性膦或Pd/三苯基膦/相转移剂为催化剂进行了羰基化和Heck反应。1烯丙基卤化物在钯的催化下，在醇-碳酸钾两相条件下常压下进行羰基化反应，得到β，γ-不饱和酯。2碘苯与2-甲基-3-丁烯-2-醇在NaOH水溶液中的反应，一锅可得丁烯内酯。3乙烯的芳基化在膦修饰的钯催化剂上，乙烯与芳基卤化物的芳基化反应很容易发生，生成二茂铁。用该方法合成了多种功能单体。

项目成果

Jitsuo Kiji: "A Convenient Route to β,γ-Unsaturated Esters without Formation of the α,β-Isomers" Bulletin of Chemical Society of Japan. 69・4. 1029-1031 (1996)

Jitsuo Kiji：“不形成 α,β-异构体的 β,γ-不饱和酯的便捷途径”日本化学会通报 69・4 (1996)。

Jitsuo Kiji, Tamon Okano, Yukiko Higashimae, Yasuyuki Fukui: "A Convenient Route to beta, gamma-Unsaturated Esters without Formation of the alpha, beta-Isomers" Bull.Chem.Soc.Jpn.69 (4). 1029-1031 (1996)

Jitsuo Kiji、Tamon Okano、Yukiko Higashimae、Yasuyuki Fukui：“不形成 α、β-异构体的 β、γ-不饱和酯的便捷途径”Bull.Chem.Soc.Jpn.69 (4)。

Jitsuo Kiji: "Building up a Conjugated System by the Palladium-Catalyzed Arylation of Ethylene (The Heck Reaction)" Macromolecular Symposia. 105. 167-171 (1996)

Jitsuo Kiji：“通过钯催化的乙烯芳基化（赫克反应）构建共轭系统”高分子研讨会。

Jitsuo Kiji: "Palladium-Catalyzed Arylation of Ethylene(The Heck Reaction)under Aqueous Conditions" Journal of Molecular Catalysis A;Chem.97. 73-77 (1995)

Jitsuo Kiji：“在水条件下钯催化的乙烯芳基化（赫克反应）”《分子催化杂志 A》；Chem.97。

Jitsuo Kiji: "Building up a Conjugated System by the Palladium-Catalyzed Arylation of Ethlene (The Heck Reaction)" Macromolecular Symposia). 105. 167-171 (1996)

Jitsuo Kiji：“通过钯催化的乙烯芳基化（赫克反应）构建共轭系统”高分子研讨会）。