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主题，包括基于酞菁的固相标记的构建，结果总结如下： 1．环氧化物向醛的区域和立体选择性重排不仅显示出高产率和选择性，而且显示出高效率。在催化中也具有出色的可重用性，这使得能够从光学活性三取代环氧化物实际合成带有立体季碳中心的对映体富集醛。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)卟啉络合物，Cr(IPP) C1，作为催化剂 Cr(TPP) Cl在低催化剂负载量下显着增强烯丙基乙烯基醚热克莱森重排中的 E/Z 选择性逆转3。我们开发了第一种利用氰乙基溴化锌实现卟啉催化单氰化和二氰化反应的方法。作为一种高效的氰化物离子源，与一系列卟啉兼容。4。该方法基于利用(2-吡啶基-二甲基甲硅烷基)甲基作为潜在甲酰基官能团的功能化卟啉的新合成概念，开发了将5, 15-取代的卟啉转化为相应的内消旋甲酰化卟啉的方法，以良好的方式提供了所需的产物。 5.一系列单官能化和双官能化的内消旋卟啉，其烷基上带有化学反应性官能团通过钯催化的Negishi交叉偶联，通过内消旋溴化前驱体与烷基锌试剂的反应，有效地合成了中间位置的取代基。6．一种基于锌卟啉二聚体和各种对映纯有机分子的新型超分子手性体系。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的手性现象。