Development of New icroencapsulated Polymer-Supported Catalysts
Development of New icroencapsulated Polymer-Supported Catalysts
批准号:
11555241
负责人:
KOBAYASHI Shu
金额:
$8.9万
依托单位:
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
项目状态:
已结题
起止时间:
1999 至 2001
中文摘要
聚合物催化剂因其易于加工、产品和催化剂易于分离、从经济角度以及在工业过程中的应用等优点得到了广泛的认可。然而,总的来说,聚合物催化剂存在制备困难、不稳定和活性低等缺点。为了解决这些问题,我们已经开发了一种新型的聚合物催化剂,称为微胶囊催化剂,这种催化剂制备容易,活性高,可回收和重复使用。开发了微胶囊四氧化三催化烯烃不对称双羟基化反应。采用微胶囊化技术,以四氧化三铯和ABS聚合物为原料,制备了催化剂。在大多数情况下,以高产率和高对映体过量获得了所需的二元醇。我们还开发了一种基于苯氧乙氧基甲基聚苯乙烯(PEM)的新型聚合物负载Os催化剂。催化剂系统不需要缓慢地添加烯烃,这是一个繁琐的过程。在有机合成中,钯催化剂在各种转化反应中有着广泛的用途,但它们价格昂贵,对空气敏感,在许多情况下无法回收。我们已经开发了三苯基膦钯,它已经成功地用于几个钯催化的反应。
英文摘要
The utility of polymer catalysts is now well-recognized because of their ease of workup and of separation of products and catalysts, from the economical point of view, and in application to industrial processes, etc. However, in general, polymer catalysts have some disadvantages such as difficult preparation, instability, and low activity. To address these issues, we have already developed new types polymer catalysts, named 'microencapsulated catalysts,' which are readily prepared, have high activity, and are recoverable and reusable.Catalytic asymmetric dihydroxylation of olefins using microencapsulated osmium tetroxide was developed. The catalyst was readily prepared from osmium tetroxide and an ABS polymer based on a microencapsulation technique. In most cases, the desired diols were obtained in high yields with high enantiomeric excesses.We have also developed a phenoxyethoxymethylpolystyrene (PEM)-based novel polymer-supported osmium catalyst. The catalyst system does not require a slow addition of olefins, which has been a tedious procedure. The catalyst was recovered quantitatively by simple filtration and reused without loss of activity.While palladium catalysts find wide-spread utility in a variety of transformations in organic synthesis, they are expensive, air-sensitive, and cannot be recovered in many cases. We have developed triphenylphosphine palladium, which has been successfully used in several palladium-catalyzed reactions.
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S.Kobayashi: "Catalytic Asymmetric Dihydroxylation of Olefines Using a Recoverable Polymer-Supported Osmium Catalyst"Journal of American Chemical Society. 121. 11229-11230 (1999)
S.Kobayashi:“使用可回收聚合物负载的锇催化剂催化烯烃的不对称二羟基化”美国化学会杂志。
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S. Kobayashi: "Microencapsulated Catalysts〜Polymer catalysts Using Microencapsulation Technique for Immobilization onto Polymers"Wakojunyakujihou. 67(JAPAN ONLY). 6-9 (1999)
S. Kobayashi:“微囊化催化剂〜利用微囊化技术固定到聚合物上的聚合物催化剂”Wakojunyakujihou 67(仅限日本)。
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S. Kobayashi, R. Akiyama: "New Methods for High-throughput Synthesis"Pure Appl. Chem.. 73. 1103-1111 (2001)
S. Kobayashi,R. Akiyama:“高通量合成的新方法”Pure Appl。
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S.Kobayashi: "Catalytic Asymmetric Dihydroxylation of Olefins Using a Recoverable and Reusable Polymer-Supported Osmium Catalyst"J. Am. Chem. Soc.. 121. 11229-11230 (1999)
S.Kobayashi:“使用可回收和可重复使用的聚合物负载锇催化剂催化烯烃的不对称二羟基化”J。
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R.Akiyama: "Microencapsulated Palladium Catalysts. Allylic Substitution and Suzuki Coupling Using a Recoverable and Reusable Polymer-Supported Palladium Catalyst"Angew. Chem., Int. Ed.. 40. 3496-3471 (2001)
R.Akiyama:“微封装钯催化剂。使用可回收和可重复使用的聚合物支撑钯催化剂的烯丙基取代和铃木偶联”Angew。
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