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Construction of Novel Chiral Host Molecule Systems Utilizing meso-Carbon Bridged Porphyrin Dimers and Their Application to Organic Synthesis

利用内消旋碳桥卟啉二聚体构建新型手性主体分子体系及其在有机合成中的应用

基本信息

批准号：
16590020
负责人：
SUDA Kohji
金额：
$ 1.98万
依托单位：
Meiji Pharmaceutical University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

A broad range of topics of porphyrin chemistry including construction of novel and synthetically useful chiral host molecule systems utilizing meso-carbon bridged porphyrin dimers were studied. The results obtained are briefly summarized as follows.(1) Catalytic and regio-and stereoselective rearrangement of epoxides to aldehydes via an alkyl migration can easily be achieved with a high valent metalloporphyrin complex, Cr(tpp)OTf, at a low catalyst loading. Since we have previously reported that Fe(tpp)X catalyzes the rearrangement of epoxides to ketones via a hydrogen mygration, ketones and aldehydes can selectively be prepared from epoxides in a highly controlled manner by the simple choice of Fe(III) and Cr(III) as a central metal ion of the porphyrin catalysts.(2) A novel and efficient recyclable catalyst system can now be realized using a phthalocyanine-based Lewis acid catalyst, Cr(PC)OTf, that can effectively promote the regio-and stereoselective rearrangement of epoxides to ald … More ehydes. This recyclable catalyst system provides an operationally simple, practical way for synthesizing optically active aldehydes from epoxides.(3) The porphyrin-based Lewis acid catalyst can effectively accelerate the rearrangement via a concerted [3,3] pathway with a minimal degree of bond ionization of the substrates, providing the corresponding Claisen products in moderate to high yields and almost perfect regioselectivity at low catalyst loading. The most notable advantage of the catalyst system is its unique stereoselectivity: Cr(TPP)Cl significantly enhances reversal of E/Z selectivity in the thermal Claisen rearrangement of allyl vinyl ethers, especially, 4,5-and 4,6-disubstituted derivatives, and dose so in a catalytic fashion.(4) Palladium-catalyzed cyanation of bromoporphyrins is now realized using cyanoethylzinc bromide as a specific cyanating agent. This new protocol provides an easy access to various cyanated Zn(II) porphyrins, including meso-mono-, meso-di-, and β-mono-cyano-substituted Zn(II) complexes.(5) A facile and efficient synthesis of meso-formyl substituted porphyrins via substitution reactions of porphyrins with silylmethyllithium reagents, especially PyMe2SiCH2Li, followed by oxidation with DDQ has been developed.(6) The porphyrin dimers that adopt a pseudocofacial conformation can effectively bind a variety of organic molecules, such as amines, alcohols, and ethers, over room temperatures. We also disclosed the use of the porphyrin dimers for the direct sensing of chiral amines and alcohols based on the CD exciton chirality method. Less

卟啉化学的一个广泛的主题，包括利用中位碳桥卟啉二聚体构建新型的和合成有用的手性主体分子系统进行了研究。所得结果简述如下。(1)用高价金属卟啉络合物Cr（tpp）OTf在低催化剂负载量下可以容易地实现环氧化物通过烷基迁移的催化和区域和立体选择性重排为醛。由于我们以前已经报道了Fe（tpp）X催化环氧化物通过氢化重排为酮，通过简单地选择Fe（III）和Cr（III）作为卟啉催化剂的中心金属离子，可以以高度受控的方式从环氧化物选择性地制备酮和醛。(2)利用酞菁基刘易斯酸催化剂Cr（PC）OTf，可以实现一种新型的和有效的可循环催化剂体系，该催化剂可以有效地促进环氧化物的区域和立体选择性重排为ALD ...更多信息伊迪斯。该催化剂体系为从环氧化物合成光学活性醛提供了一种操作简单、实用的方法。(3)基于卟啉的刘易斯酸催化剂可以有效地通过协同的[3，3]途径加速重排，并且具有最小程度的底物的键电离，从而在低催化剂负载量下以中等至高的产率和几乎完美的区域选择性提供相应的Claisen产物。该催化剂体系最显著的优点是其独特的立体选择性：Cr（TPP）Cl显著增强了烯丙基乙烯基醚，特别是4，5-和4，6-二取代衍生物的热Claisen重排反应中E/Z选择性的逆转，并以催化方式发挥作用。(4)溴卟啉的钯催化氰化反应是以氰乙基溴化锌为氰化剂实现的。这种新的方案提供了一个容易获得的各种氰化锌（II）卟啉，包括meso-单-，meso-二-，和β-单氰基取代的锌（II）配合物。(5)通过卟啉与硅基甲基锂试剂，特别是PyMe_2SiCH_2Li的取代反应，然后用DDQ氧化，合成了meso-甲酰基取代卟啉。(6)卟啉二聚体采用伪共面构象，可以在室温下有效地结合各种有机分子，如胺、醇和醚。我们还公开了卟啉二聚体用于基于CD激子手性方法的手性胺和醇的直接传感的用途。少