Development of Amphiphilic Resin-Supported Catalysts Realizing Water-Based Organic Synthesis

实现水基有机合成的两亲性树脂负载催化剂的开发

• 批准号: 11470472
• 负责人: UOZUMI Yasuhiro
• 金额: $ 2.69万
• 依托单位: Institute for Molecular Science (2000)Nagoya City University (1999)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11470472/
• 关键词: ansition metal catalysts; palladium-phosphine complexes; amphiphilic solid support; organic transformation in water; PS-PEG resin; palladium catalysis; PS-PEG レジン

New amphiphilic resin-supported triarylphosphines (PEP) were designed and prepared on polyethylene glycol-polystyrene graft copolymer (PEG-PS). The PEG-PS resin-supported palladium-monophosphine complex Pd(PEP) was readily prepared by treatment of PEP with an excess amount of di(m-chloro)bis(h3-allyl) dipalladium(II) ([PdCl(h3-C3H5)]2) (Pd/P > 1/1) followed by removal of unimmobilized [PdCl(h3-C3H5)]2 by washing. Palladium complexe Pd(PEP) catalyzed allylic substitution of 3-acetoxy-1,3-diphenyl-1-propene and cinnamyl acetate with various nucleophiles including 1,3-dicarbonyl compounds, amino acids, sodiumazide, and sodium sulfinate, to give quantitative yields of corres ponding allylic substituted products in water.The hydroxycarbonylation reaction of aryl or alkenyl halides also took place in aqueous alkaline solution under an atmospheric pressure of carbon monoxide at 25 。C in the presence of 3 mol % palladium of an amphiphilic resin-supported palladium-phosphine complexe bound to a … More polyethylene glycol-polystyrene graft copolymer (PEG-PS resin) (Pd(PEP). The reaction of aryl halides gave correspond-ing benzoic acids in quantitative yields. Pd-PEP also catalyzedHeck reaction of iodobenzene with acrylic acid to give cinnamic acid in 92%yield. No organic solvent was used for the reactions and no chromatographical purification was re-quired to obtain the products. The resin-supported catalyst was recovered by filtration and reused. No loss of catalytic activity was observed during 30 runs. The cross-coupling reaction of aryl halides or allyl acetates with arylboronic acids or sodium tetraphenylborate was catalyzed in water by the Pd(PEP) catalyst. The reaction of aryl halides with arylboron reagents in the presence of 2 mol% palladium of Pd(PEP) in aqueous alkaline solution at 25 。C gave corresponding biphenyl derivatives in high yields. Pd(PEP) also catalyzed allylic arylation of allyl acetates (including 1,3-disubstituted allyl acetates and cyclic allyl acetates) with arylboron reagents in water under the similar reaction conditions to give 80-99% yield of allylarenes. Less

在聚乙二醇-聚苯乙烯接枝共聚物（PEG-PS）上设计并制备了新型两亲性树脂负载三芳基膦（PEP）。用过量的二（m-氯）双（h3-烯丙基）双钯（II） （[PdCl(h3-C3H5)]2） （Pd/P > 1/1）处理PEP，然后通过洗涤去除未固定的[PdCl(h3-C3H5)]2，制备了PEG-PS树脂负载的钯-单膦配合物Pd（PEP）。钯络合物Pd（PEP）催化3-乙酰氧基-1,3-二苯基-1-丙烯和肉桂乙酸酯与各种亲核试剂（包括1,3-二羰基化合物、氨基酸、肼钠和亚硫酸钠）的烯丙基取代，定量地给出了在水中聚合烯丙基取代产物的收率。芳基卤化物和烯基卤化物在25大气压下的碱性水溶液中也发生了羟基羰基化反应。在3mol %钯存在下，两亲性树脂负载的钯-膦络合物结合到…More聚乙二醇-聚苯乙烯接枝共聚物（PEG-PS树脂）（Pd(PEP)）。芳基卤化物反应得到相应的苯甲酸定量产率。Pd-PEP还催化了碘苯与丙烯酸的heck反应，产率为92%。该反应不使用有机溶剂，也不需要进行色谱纯化。树脂负载型催化剂经过滤回收再利用。在30次运行中没有观察到催化活性的损失。用Pd（PEP）催化剂在水中催化芳基卤化物或醋酸烯丙酯与芳基硼酸或四苯基硼酸钠的交叉偶联反应。在2mol % Pd（PEP）存在下，芳基卤化物与芳基硼试剂在25℃碱性水溶液中的反应。C高产出相应的联苯衍生物。在类似的反应条件下，Pd（PEP）还在水中与芳基硼试剂催化醋酸烯丙酯（包括1,3-二取代醋酸烯丙酯和环醋酸烯丙酯）的烯丙基芳基化反应，得到80-99%的丙烯芳烃收率。少

项目成果

林民生: "Asymmetric Hydrosilylation of Styrenes Catalyzed by Palladium-MOP Complexes : Ligand Modification and Mechanistic Studies"J.Org.Chem.. 66. 1441-1449 (2001)

Tamio Hayashi：“钯-MOP 配合物催化的苯乙烯不对称氢化硅烷化：配体修饰和机理研究”J.Org.Chem.. 66. 1441-1449 (2001)

Tamio Hayashi: "Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes"Chem.Lett.. 1272-1273 (2000)

Tamio Hayashi：“用于钯催化苯乙烯不对称氢化硅烷化的手性单齿膦 (MOP) 配体的修饰”Chem.Lett.. 1272-1273 (2000)

Kazutaka Shibatomi: "Michael Reactions in Water Using Amphiphilic Resin-Supported Quaternary Ammonium Hydroxides"Synlett.. 11. 1643-1645 (2000)

Kazutaka Shibatomi：“使用两亲性树脂支持的季铵氢氧化物在水中进行迈克尔反应”Synlett.. 11. 1643-1645 (2000)

魚住泰広: "Michael Reactions in Water Using Amphiphilic Resin-Supported Quaternary Ammonium Hydroxides"Synlett.. 11. 1643-1645 (2000)

Yasuhiro Uozumi：“使用两亲性树脂支持的季铵氢氧化物在水中进行迈克尔反应”Synlett.. 11. 1643-1645 (2000)

魚住泰広: "A parallel preparation of a bicyclic N-chiral amine library and its use for chiral catalyst screening"Tetrahedron Letters. 42. 407-410 (2001)

Yasuhiro Uozumi：“双环 N-手性胺库的平行制备及其在手性催化剂筛选中的应用”Tetrahedron Letters，42. 407-410 (2001)。