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Construction of Phthalocyanine-Based Solid Phase Tags and Their Utility for Synthetic Organic Chemistry

酞菁基固相标签的构建及其在有机合成化学中的应用

基本信息

批准号：
17590018
负责人：
TAKANAMI Toshikatsu
金额：
$ 2.44万
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：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

A broad range of topics of porphyrin and phthalocyanine chemistry including construction of phthalocyanine-based solid phase tags were studied. The results obtained are summarized as follows.1. A metallophthalocyanine complex, Cr(TBPC) OTf works as an efficient Lewis acid catalyst that can promote the regio- and stereoselective rearrangement of epoxides to aldehydes. It shows not only high efficiencies in yields and selectivities, but also excellent reusability, in the catalysis, which enables practical synthesis of enantio-enriched aldehydes bearing a stereogenic quatemary carbon center from optically active tri-substituted epoxides.2 The catalytic Z-selective Claisen rearrangement of simple aliphatic allyl vinyl ethers can be realized using a chromium(III) porphyrin complex, Cr(IPP) C1, as a catalyst Cr(TPP) Cl significantly enhances reversal of E/Z selectivity in the thermal Claisen rearrangement of allyl vinyl ethers at low catalyst loading3. We have developed the first method that … More achieves catalytic mono-and dicyanation of porphyrins. These palladium-catalyzed cyanation reactions utilizing cyanoethyl zinc bromide as an efficient cyanide ion source are compatible with an array of porphyrins.4. A simple one-pot procedure that converts 5, 15-substituted porphyrins into the corresponding meso formylated porphyrins has been developed. The method, based on a new synthetic concept for functionalized porphyrins utilizing the(2-pyridyl-dimethylsilyl) methyl group as a latent formyl functionality, affords desired product in good yield.5. A series of mono-and bis-functionalized meso-substituted porphyrins bearing chemically reactive functional groups in the alkyl substituents at the meso positions were efficiently synthesized by the reactions of meso-brominated precursors with alkylzinc reagents via palladium-catalyzed Negishi cross-coupling.6. A new supramolecular chirogenic system on the basis of zinc porphyrin dimers and various enantiopure organic molecules, which was specifically designed for investigation of the chirogenic phenomenon upon extremely weak interaction modes and marginal chiroptical responses, is studied. Less

研究了卟啉和酞菁化学的广泛课题，包括酞菁基固相标记物的构建。主要研究结果如下：1.金属酞菁配合物Cr（TBPC）OTf作为一种有效的刘易斯酸催化剂，可以促进环氧化物区域和立体选择性重排成醛。它不仅在产率和选择性方面表现出高效性，而且在催化中具有优异的可重复使用性，这使得能够从光学活性的三取代环氧化物实际合成具有立体四元碳中心的对映体富集的醛。2简单脂肪族烯丙基乙烯基醚的催化Z-选择性克莱森重排可以使用铬（III）卟啉配合物Cr（IPP）C1实现，作为催化剂，Cr（TPP）Cl在低催化剂负载下显著增强烯丙基乙烯基醚的热克莱森重排中E/Z选择性的逆转3。我们开发了第一种方法， ...更多信息实现卟啉的催化单氰化和双氰化。这些钯催化的氰化反应利用氰乙基溴化锌作为有效的氰离子源是兼容的卟啉阵列。发展了一种简单的一锅法将5，15-取代卟啉转化为相应的meso甲酰化卟啉。该方法基于一种新的功能化卟啉的合成概念，利用（2-吡啶基-二甲基甲硅烷基）甲基作为潜在的甲酰基官能团，以良好的产率提供所需的产物。通过钯催化下的Negishi交叉偶联反应，将meso溴化前体与烷基锌试剂反应，合成了一系列在meso位烷基取代基上带有化学活性官能团的单、双功能化meso取代卟啉。研究了一种新的基于锌卟啉二聚体和各种对映体纯有机分子的超分子手性体系，该体系是专门设计用于研究极弱相互作用模式和边缘手性光学响应下的手性现象的。少