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Development of catalytic organic reactions in aqueous media

水介质中催化有机反应的进展

基本信息

批准号：
15390003
负责人：
MANABE Kei
金额：
$ 8.96万
依托单位：
RIKEN (2005-2006)The University of Tokyo (2003-2004)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2006
项目状态：
已结题

项目摘要

Recently, use of water as a reaction solvent has received considerable attention in synthetic organic chemistry for several reasons. First, water is a cheap, safe, and environmentally benign solvent when compared with organic solvents, which are normally used for organic reactions. Use of water will reduce the use of harmful organic solvents and is regarded as an important research topic in green chemistry. Second, in aqueous reactions, it is unnecessary to dry solvents, substrates, and reagents before use. Thus, consumption of drying agents, energy, and time can be reduced. Third, water has unique physical and chemical properties, and by utilizing these it would be possible to realize reactivity or selectivity that cannot be attained in organic solvents.Although various efficient catalytic systems in water have been developed so far, there are still many types of reactions which are difficult to carry out in water. The aim of this research is to develop efficient catalytic organic reactions in aqueous media.The following are the main results obtained during the research period.(1) Highly hydrophobic polymer-supported acid catalysts that can be used for various reactions in water were developed.(2) Palladium-catalyzed allylic substitution reactions of allyl alcohols in water were developed.(3) It was found that Fe(III) ion was effective for diastereoselective Mukaiyama aldol reactions in aqueous media.(4) Catalytic asymmetric hydroxymethylation of silyl enol ethers in aqueous media was developed.(5) Catalytic asymmetric Mannich-type reactions of hydrazones in water were developed.(6) Two-step repetitive synthesis of functionalized oligoarenes was achieved. The efficient methods for the synthesis using a water-THF mixed solvent system were developed.

近来，由于几个原因，在合成有机化学中使用水作为反应溶剂受到相当大的关注。首先，与通常用于有机反应的有机溶剂相比，水是一种便宜、安全和环境友好的溶剂。水的利用将减少有害有机溶剂的使用，被视为绿色化学的重要研究课题。其次，在水性反应中，在使用前不需要干燥溶剂、底物和试剂。因此，可以减少干燥剂、能量和时间的消耗。第三，水具有独特的物理和化学性质，利用这些性质可以实现在有机溶剂中无法实现的反应性和选择性。虽然目前已经开发出各种高效的水中催化体系，但仍有许多反应难以在水中进行。本研究的目的是开发水相介质中高效的有机催化反应，在研究期间取得了以下主要成果。(1)开发了可用于水中各种反应的高疏水性聚合物负载酸催化剂。(2)研究了钯催化的烯丙醇在水中的烯丙基取代反应。(3)结果表明，Fe（III）离子对非对映选择性的Mukaiyama aldol反应是有效的. (4)研究了水相中硅烯醇醚的催化不对称羟甲基化反应。(5)研究了水溶液中腙的不对称Mannich型催化反应。(6)实现了功能化低聚芳烃的两步重复合成。发展了水-四氢呋喃混合溶剂体系的合成方法。